WO2016136790A1

WO2016136790A1 - Resin supply material, preform, and method for producing fiber-reinforced resin

Info

Publication number: WO2016136790A1
Application number: PCT/JP2016/055377
Authority: WO
Inventors: 大洋竹原; 清家　聡; 本間　雅登; 聖藤岡; 里美松尾
Original assignee: 東レ株式会社
Priority date: 2015-02-27
Filing date: 2016-02-24
Publication date: 2016-09-01
Also published as: EP3263630A1; EP3263630A4; TWI699270B; TWI721909B; TW202039197A; KR20170123318A; JP6720868B2; JPWO2016136790A1; CN107250224A; TW201714722A; US10822463B2; EP3263630B1; ES2901054T3; US20180066118A1

Abstract

This resin supply material is for use in the molding of a fiber-reinforced resin. The resin supply material comprises a continuous porous body and a resin. The bending resistance Grt of the continuous porous body at 23 °C is 10 mN∙cm or more and the bending resistance ratio Gr represented by the following formula is 0.7 or less: Gr = Gmt/Grt, wherein Gmt is the bending resistance of the continuous porous body at 70 °C. The present invention makes it possible to provide: a resin supply material having excellent handling properties, resin-bearing properties, and mechanical properties in a fiber-reinforced resin; and a method for producing a fiber-reinforced resin using the resin supply material.

Description

Resin supply material, preform, and method for producing fiber reinforced resin

The present invention relates to a resin supply material, a preform, and a method for producing a fiber reinforced resin.

Since fiber reinforced resin has excellent specific strength and specific rigidity, it is widely used in applications such as aircraft, automobiles, sports, and electric / electronic parts. In recent years, it has been used in industries such as windmill blades, pressure vessels, and building reinforcement materials. Application is also progressing in the field. Particularly in industrial applications such as automobiles and electrical / electronic parts, there is an increasing demand for a high-speed molding process of fiber reinforced resin. In addition, in the use of electric / electronic parts, the amount of heat generated by the parts is increasing with downsizing and high performance. When the calorific value of the electronic component increases, the temperature inside the electronic component or device rises, and the heat may reduce the function of the electronic component or device, cause malfunction, or damage. Therefore, a material having excellent thermal conductivity is demanded.

Examples of high-speed molding methods for fiber reinforced resins include the RTM (resin transfer molding) method (Patent Document 1) and the RFI (resin film infusion) method (Patent Document 2). In the RTM method, a preform in which a dry base material (reinforced fiber base material not containing resin) is first formed into a predetermined shape is manufactured, and this is placed in a mold, and a low-viscosity liquid thermosetting resin is made into a metal mold. FRP (fiber reinforced plastic) member is molded by pouring into a mold and heat curing. Since a dry substrate is used, a three-dimensional complicated shape can be formed. However, since the RTM method requires a resin injection step, a molding auxiliary material such as a tube or pipe used in the injection step is required. In addition, in addition to the resin that becomes the molded product, a lot of useless resin that remains in the injection path or the like is generated, resulting in a cost increase. Further, in the case of a thermosetting resin, the resin cannot be reused, and cleaning for each batch requires labor, resulting in an increase in cost. There is also a drawback that traces of the injection port and the suction port remain in the molded member. Furthermore, since liquid resin is handled at room temperature, there is a problem that the site is often contaminated with resin leaking from containers and piping.

In the RFI method, a resin film made of a reinforcing fiber base material and an uncured thermosetting resin is placed in a mold, the resin film is melted by heating, impregnated into the reinforcing fiber base material, and then cured. Since the thermosetting resin that is liquid at room temperature is not used as in the RTM method, the site is less likely to get dirty, and it is possible to save the trouble of resin preparation. However, since the thermosetting resin used in the RFI method is in the form of a film and has low rigidity, there is a problem that handling property is poor, and it takes time and labor to arrange the mold.

Patent Documents

3 and 4 use an impregnated body in which a thermosetting resin that is liquid at room temperature is sucked into a soft support (described as a resin support in Patent Document 3 and a preform in Patent Document 4). A fiber reinforced resin molding method using SMC (Sheet Molding Compound) has been proposed in Japanese Patent Application Laid-Open No. 2005-26883.

Japanese Patent Laid-Open No. 2003-71856 JP 2003-11231 A Japanese Patent Laid-Open No. 2002-234078 JP 2006-305867 A JP 2008-246981 A

After the impregnated body in which the resin of

Patent Documents

3 and 4 is sucked is laminated with a dry base material, a structural member can be manufactured by heating and pressing in a mold and impregnating the reinforcing fiber base material with a thermosetting resin in the impregnated body. Since the carrier is impregnated with the resin, it can be said that the impregnated body is excellent in handleability. However, there is no limitation on the mechanical properties of the carriers used, and there is a problem that wrinkles occur due to breakage and deflection of the carriers when tension is applied during transportation and lamination of these carriers. Further, when such a carrier having low mechanical properties is present in the fiber reinforced resin, there is a concern that the mechanical properties of the fiber reinforced resin are deteriorated. In addition, the impregnated material used has a low thermal conductivity, and when a fiber reinforced resin is used, there is a problem that desired physical properties cannot be obtained. Further, since the impregnated material used has a low thermal conductivity, there are problems that temperature unevenness occurs in the material at the time of molding and that it takes time to mold a thick material.

In addition, the purpose of using the molding method of Patent Document 5 is to smoothen the surface of the molded product by suppressing the formation of dents by interposing a non-impregnated base material between the prepreg layers. Another object is to obtain a molded article having good appearance quality. Therefore, the fiber content of the prepreg is high, and the rate of change of the fiber content before and after molding is small. It is difficult to use an unimpregnated base material having a high basis weight for improving the mechanical properties of the fiber reinforced resin or to apply the resin supply material to uneven thickness molding.

The present invention has been made in view of the above, and an object thereof is a resin supply material excellent in handling property, resin supportability, and mechanical properties in a fiber reinforced resin, and a fiber reinforced resin using the resin supply material. It is in providing the manufacturing method of.

Another object of the present invention is to provide a resin supply material excellent in resin supportability, handleability, and thermal conductivity, and a method for producing a fiber reinforced resin using the resin supply material.

The resin supply material according to the first aspect of the present invention is a resin supply material used for molding a fiber reinforced resin, and is composed of a continuous porous body and a resin, and the bending resistance Grt of the continuous porous body at 23 ° C. Is 10 mN · cm or more, and the bending resistance ratio Gr represented by the following formula is 0.7 or less.
Gr = Gmt / Grt
Gmt: Bending softness of continuous porous body at 70 ° C

The resin supply material according to the second aspect of the present invention is a resin supply material used for molding a fiber reinforced resin, which is composed of a continuous porous body and a resin, and has a tensile strength σrt of the continuous porous body at 23 ° C. The tensile strength ratio σr expressed by the following formula is 0.5 or more.
σr = σmt / σrt
σmt: Tensile strength of continuous porous body at 130 ° C

The resin supply material according to the third aspect of the present invention is a resin supply material used for molding a fiber reinforced resin, and includes a continuous porous body and a resin, and the thermal conductivity of the material forming the continuous porous body. Is 1.2 W / m · K or more, and / or a continuous porous body, a resin, and a filler having a thermal conductivity of 1.2 W / m · K or more.

The preform according to the present invention includes the resin supply material according to the present invention and a base material.

In the method for producing a fiber reinforced resin according to the present invention, the preform according to the present invention is heated and pressurized to supply the resin from the resin supply material to the base material and to perform molding.

According to the present invention, it is possible to provide a resin supply material that is excellent in handleability, resin supportability, and mechanical properties in a fiber reinforced resin, and a method for producing a fiber reinforced resin using the resin supply material.

According to the present invention, it is possible to provide a resin supply material excellent in resin supportability, handleability, and thermal conductivity, and a method for producing a fiber reinforced resin using the resin supply material.

FIG. 1 is a schematic diagram showing the configuration of the resin supply material of the present invention. FIG. 2 is a schematic diagram illustrating a situation in which the continuous porous body used in the present invention is transported, a schematic diagram illustrating a case where the continuous porous body satisfying the requirements of the present invention is used, and the requirements of the present invention are not satisfied. It is a schematic diagram which shows the case where a continuous porous body is used. FIG. 3 is a schematic diagram illustrating a situation in which both ends of a continuous porous body used in the present invention are gripped and transported, a schematic diagram illustrating a case where a continuous porous body that satisfies the requirements of the present invention is used, and It is a schematic diagram which shows the case where the continuous porous body which does not satisfy | fill the requirements is used. FIG. 4 is a schematic cross-sectional view showing a cantilever type testing machine for evaluating the bending resistance in the present invention, and a schematic view showing a state in which the bending resistance of the continuous porous body in the present invention is being evaluated.

[First embodiment]
The present invention is a resin supply material comprising a continuous porous body and a resin. Moreover, as shown in FIG. 1, this invention is the manufacturing method of the fiber reinforced resin using the preform 3 containing this resin supply material 1 and the base material 2, and the preform 3. As shown in FIG. First, each constituent material will be described.

<Continuous porous body>
The continuous porous body in the present invention requires that the bending resistance Grt of the continuous porous body at 23 ° C. is 10 mN · cm or more for the purpose of expressing the handleability of the resin supply material 1 and The bending resistance ratio Gr described later needs to be 0.7 or less.

The term “continuous porous body” as used herein refers to a porous body in which enclosing pores are connected to each other, and a gas such as air or a liquid such as water is permeable in the thickness direction of the porous body. It is. Whether gas or liquid is permeable can be determined by JIS-L1096 (2010) “Fabric and knitted fabric test method” and JIS-R1671 (2006) “Water permeability and hydraulic equivalent diameter test method of fine ceramic porous material”. Can be confirmed.

The term “bending softness” as used herein refers to the deflection of a continuous porous material when evaluated with reference to the measuring method for bending softness specified in JIS-L1913 (2010) “General nonwoven fabric testing method”. The details will be described later. The “bending softness ratio” referred to here is the ratio of the bending resistance Gmt at 70 ° C. to the bending resistance Grt at 23 ° C. and can be expressed by the following equation.

Gr = Gmt / Grt

When the continuous porous body 5, the resin supply material 1, and the preform 3 containing them are transported and laminated by using the arm 4 as shown in FIG. If it is high, the amount of deformation of the resin supply material 1 is small and it can be easily transported and laminated (FIG. 2 (ii)). On the other hand, when the continuous porous body 5 having a low bending resistance is used as shown in FIG. 2 (iii), the resin supply material 1 is greatly deformed, and the arm 4 and the other material are prevented from coming into contact with the other material. It can be a factor of enlarging the apparatus, such as increasing the clearance between them and increasing the number of claws 6 of the arm 4. For this reason, from the viewpoint of improving handleability, the bending resistance of the continuous porous body at 23 ° C. is preferably 30 mN · cm or more, and more preferably 50 mN · cm or more.

On the other hand, the bending resistance Gmt at 70 ° C. represents the ease with which the resin supply material 1 made of a continuous porous material and a resin or the preform 3 including the resin supply material 1 is molded, and is a ratio thereof. The bending resistance ratio Gr (= Gmt / Grt) needs to be 0.7 or less. By using such a resin supply material 1 made of a continuous porous body and a resin, it is easy to handle during transportation and lamination, and is necessary for producing a fiber reinforced resin that is flexible and highly moldable during molding. Therefore, it is possible to provide the resin supply material 1 that satisfies both of the required characteristics.

The bending resistance and the basis weight are calculated from the bending length and the basis weight. For example, if the continuous porous body has the same bending length, the higher the basis weight, the higher the bending resistance and the greater the amount of resin that can be supported. preferable. In the case of the same basis weight, a longer bending length is preferable from the viewpoint of increasing the bending resistance and improving the handleability. At this time, the bending length Crt at 23 ° C. is preferably 5 cm or more from the viewpoint of handleability, more preferably 8 cm or more, and further preferably 10 cm or more.

In the present invention, the minimum tensile strength σmin of the continuous porous body is preferably 3 MPa or more. For example, when the both ends of the continuous porous body 5 are held by the clamps 7 as shown in FIG. From the viewpoint of preventing breakage due to tension or self-weight (FIG. 3 (iii)), it is more preferably 5 MPa or more, and further preferably 8 MPa or more. By using such a material, it is possible to apply a high tension when gripping, and in the preform 3 including the resin supply material 1, it is possible to arrange a large number of base materials 2. The degree of freedom can be increased.

The tensile strength ratio σr (= σo / σmin) between the minimum tensile strength σmin of the continuous porous body and the tensile strength σo in the direction orthogonal to the direction of the minimum tensile strength is 1.0 to 1.2. It is preferable to be within the range. By making such a continuous porous body, it is not necessary to consider the direction of the material during lamination, the degree of design freedom and productivity can be improved, and the resulting fiber reinforced resin exhibits isotropic mechanical properties Is possible. At this time, the tensile strength ratio is more preferably in the range of 1.0 to 1.1, and further preferably in the range of 1.0 to 1.05.

The continuous porous body in the present invention is preferably formed of reinforcing fibers, and is not particularly limited, but may be fibers made of a material having higher mechanical properties than the resin that becomes the matrix resin. Specific examples include resin fibers such as polyphenylene sulfide, polyamide, polycarbonate, and polyimide, and glass fibers, carbon fibers, aramid fibers, and metal fibers. Among these, glass fibers, carbon fibers, aramid fibers, and metals More preferably, it is at least one selected from fibers. Among these reinforcing fibers, carbon fibers are more preferable. The type of carbon fiber is not particularly limited. For example, carbon fibers such as polyacrylonitrile (PAN), pitch, and rayon can be preferably used from the viewpoint of improving mechanical properties and reducing the weight of the fiber reinforced resin. You may use together 1 type, or 2 or more types. Among these, PAN-based carbon fibers are more preferable from the viewpoint of the balance between strength and elastic modulus of the obtained fiber reinforced resin. The single fiber diameter of the reinforcing fiber is preferably 0.5 μm or more, more preferably 2 μm or more, and further preferably 4 μm or more. The single fiber diameter of the reinforcing fiber is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. The strand strength of the reinforcing fiber is preferably 3 GPa or more, more preferably 4 GPa or more, and further preferably 4.5 GPa or more. The strand elastic modulus of the reinforcing fiber is preferably 200 GPa or more, more preferably 220 GPa or more, and further preferably 240 GPa or more.

The reinforcing fiber may be a continuous fiber used for a unidirectional base material or a woven base material, but a discontinuous fiber is preferable from the viewpoint of resin supply. A web dispersed in a bundle shape or a single fiber shape and having voids impregnated with resin between the fibers is preferable. There are no restrictions on the form and shape of the web. For example, reinforcing fibers are mixed with organic fibers, organic compounds or inorganic compounds, reinforcing fibers are bonded with other components, or reinforcing fibers are bonded to resin components. It may be done. From the viewpoint of easily producing a web in which fibers are dispersed, a base material in which reinforcing fibers are sufficiently opened and single fibers are bonded with a binder made of an organic compound in a non-woven form obtained by a dry method or a wet method. Can be illustrated as a preferred shape.

It is preferable that the fibers of the continuous porous body formed by the reinforcing fibers preferably used in the present invention are bonded with a binder. Thereby, handling property, productivity, and workability are improved, and the network structure of the continuous porous body can be maintained. The binder is not particularly limited, but polyvinyl alcohol, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polycarbonate resin, styrene resin, polyamide resin, polyester. Resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polypropylene resin, polyethylene resin, fluororesin, thermoplastic acrylic resin, thermoplastic polyester resin, thermoplastic polyamideimide resin, acrylonitrile-butadiene copolymer Polymers such as polymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, urethane resins, melamine resins, urea resins, thermosetting type Le resins, phenol resins, epoxy resins, thermosetting resins such as thermosetting polyesters is preferably used. From the viewpoint of the mechanical properties of the resulting fiber reinforced resin, at least one function selected from an epoxy group, a hydroxyl group, an acrylate group, a methacrylate group, an amide group, a carboxyl group, a carboxylic acid, an acid anhydride group, an amino group, and an imine group A resin having a group is preferably used. These binders may be used alone or in combination of two or more. The adhesion amount of the binder is preferably 0.01% or more, more preferably 0.1% or more, and further preferably 1% or more. Further, the adhesion amount of the binder is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. If the adhesion amount of the binder exceeds 20%, the drying process may take time or the resin impregnation property may be lowered. On the other hand, when the adhesion amount of the binder is less than 0.01%, when the web made of the reinforcing fiber of the present invention is used for the continuous porous body, it is difficult to maintain the form and the handling property may be deteriorated. In addition, the adhesion amount of a binder can be measured by a mass difference before and after the binder application or a baking method.

The average fiber length of the reinforcing fibers is preferably 0.1 mm or more, more preferably 1 mm or more, and further preferably 2 mm or more. The average fiber length of the reinforcing fibers is not particularly limited, but is preferably 100 mm or less, more preferably 50 mm or less, and even more preferably 10 mm or less, from the viewpoint of isotropic properties of the continuous porous body and dispersibility of the reinforcing fibers. The average fiber length can be measured by, for example, extracting the reinforcing fibers directly from the reinforcing fiber base material, or dissolving them using a solvent that dissolves only the resin of the prepreg, and filtering the remaining reinforcing fibers to measure by microscopic observation. There is a method to do (dissolution method). In the case where there is no solvent for dissolving the resin, there is a method (burn-off method) in which only the resin is burned off in a temperature range where the reinforcing fibers are not oxidatively reduced, and the reinforcing fibers are separated and measured by microscopic observation. The measurement can be carried out by randomly selecting 400 reinforcing fibers, measuring the length to the 1 μm unit with an optical microscope, and measuring the fiber length and its ratio. In addition, when comparing the method of extracting the reinforcing fiber directly from the reinforcing fiber substrate and the method of extracting the reinforcing fiber from the prepreg by the burning method or the dissolution method, the results obtained by appropriately selecting the conditions There is no special difference.

Mass per unit area of continuous, porous body in the present invention (mass per unit area) is preferably from 10 g / ^{m 2} or more, 100 g / ^{m 2} or more, more preferably, 300 g / ^{m 2} or more is more preferable. If the mass per unit area is less than 1 g / m ² , the resin supportability is lowered, and the amount of resin necessary for molding may not be supported. Furthermore, in the process of manufacturing the resin supply material 1, the handleability may be poor and workability may be reduced.

<Resin>
The elastic modulus Ert at 23 ° C. of the resin in the present invention is preferably 1 MPa or more, more preferably 3 MPa or more from the viewpoint of handleability of the resin supply material 1 at 23 ° C., and further 5 MPa or more. preferable.

The type of resin used in the present invention is not particularly limited, and any of a thermosetting resin and a thermoplastic resin can be used. As the thermosetting resin, at least one selected from epoxy resin, vinyl ester resin, phenol resin, thermosetting polyimide resin, polyurethane resin, urea resin, melamine resin, and bismaleimide resin is preferably used. In addition to a single epoxy resin, a copolymer of epoxy resin and a thermosetting resin, a modified product, and a resin blended with two or more types can also be used. As thermoplastic resins, polypropylene, polyethylene, polycarbonate, polyamide, polyester, polyarylene sulfide, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether sulfone, polyimide, polyamide imide, polyether imide, At least one selected from polysulfone is preferably used, and a cyclic oligomer that is a precursor of any of these resins is also preferably used.

As with the continuous porous body, the resin is preferably easy to handle at 23 ° C., soft and easy to mold, and preferably has a lower elastic modulus at 70 ° C. than 23 ° C.

The viscosity at the time of resin impregnation (molding) in the present invention is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less, and even more preferably 10 Pa · s or less. When it exceeds 1000 Pa · s, there is a concern that the base fiber 2 described later is not sufficiently impregnated with the resin, so that the resulting fiber reinforced resin is not impregnated and voids are generated.

<Resin supply material>
The resin supply material 1 according to the present invention is excellent in transportability in the state of the preform 3 including only the resin supply material 1 or the base material 2, handling property at the time of lamination and moldability at the time of molding, and fiber reinforcement. It is necessary to carry a resin to be a matrix resin of the conductive resin and supply the resin to the base material 2 at the time of molding. 0.03 or more is preferable, as for the resin mass change rate P of the resin supply material 1 before and behind shaping | molding represented by following Formula, 0.05 or more are more preferable, and 0.08 or more are further more preferable. Further, in order to obtain a fiber reinforced resin with less voids due to the resin flowing from the resin supply material 1 to the base material 2, the change rate P is preferably 0.99 or less, more preferably 0.7 or less, and 5 or less is more preferable. The resin mass Wr1 in the resin supply material 1 before molding and the resin mass Wr2 in the resin supply material 1 after molding are JIS-K7075 (1991) “Fiber content rate and void ratio test method of carbon fiber reinforced plastic”. Required in compliance with In the case of the preform 3 containing the resin supply material 1, only the resin supply material (A) is taken out by polishing or cutting, and JIS-K7075 (1991) “Fiber content rate and void ratio test of carbon fiber reinforced plastic” It can also be determined in accordance with “Method”.

P = Wr2 / Wr1
Wr1: Resin mass in the resin supply material before molding (g)
Wr2: Resin mass in the resin supply material after molding (g)

By using such a resin supply material 1, it becomes possible to supply the resin to more base materials 2, and the design flexibility and mechanical characteristics of the fiber reinforced resin can be enhanced.

In addition, in order to form a fiber reinforced resin with less voids by the resin flowing (impregnated) from the resin supply material 1 to the base material 2, the continuous porous material in the resin supply material 1 before and after molding represented by the following formula: The volume content change rate Q of the body is preferably 1.1 or more, more preferably 1.3 or more, and even more preferably 1.5 or more. Further, the rate of change Q is preferably 30 or less, more preferably 15 or less, and even more preferably 5 or less so that the resin does not flow out as much as possible and flows efficiently from the resin supply material 1 to the base material 2. The volume content Vpt of the continuous porous body after molding is determined in accordance with JIS-K7075 (1991) “Test method for fiber content and void ratio of carbon fiber reinforced plastic”. Further, instead of the method for specifying the volume content Vpt, the thickness T (unit: mm, measured value) and the basis weight Faw (unit: g / m ² , catalog or measured value) of the continuous porous body, continuous porous The volume content Vpt may be determined by the following formula using the density ρ of the body (unit: g / cm ³ , catalog or measured value). The thickness T is obtained from the average thickness of any 10 points in the range of 50 mm length and 50 mm width of the resin supply material 1. The thickness direction is a direction orthogonal to the contact surface with the base material 2 used for the preform.

Q = Vpt / Vpi
Vpi: Volume content (%) of continuous porous body before molding
Vpt: Volume content (%) of the continuous porous body after molding

In addition, it can be said that the resin supply material 1 in the present invention satisfies the preferable range of the change rate P and the preferable range of the change rate Q simultaneously.

The production method of the resin supply material 1 is not particularly limited, but the continuous porous body is immersed in a liquid resin and impregnated with the resin, or the continuous porous body is heated under heating conditions in order to reduce the viscosity of the resin. A method of impregnating resin by pressurizing the body and resin using a press plate or roll, etc., enclosing the continuous porous body and resin under reduced pressure conditions, and replacing the air present in the continuous porous body with resin For example, a method of impregnating by impregnation.

The resin supply material 1 in the present invention is preferably in the form of a sheet, and the sheet thickness at that time is preferably 0.5 mm or more, more preferably 1 mm or more from the viewpoints of handleability, resin supply properties, and mechanical properties. More preferably, it is 1.5 mm or more. Moreover, from the viewpoint of design freedom and formability, the thickness is preferably 100 mm or less, more preferably 60 mm or less, and even more preferably 30 mm or less.

The mass content Wpi of the continuous porous body of the resin supply material 1 in the present invention is preferably 0.5% or more, more preferably 1.0% or more, and further preferably 1.5% or more. If the mass content Wpi is less than 0.5%, the amount of the resin is too much for the continuous porous body, and the resin cannot be supported on the continuous porous body, or a large amount of resin flows to the outside during molding. There are things to do. Although not particularly limited, the mass content Wpi is preferably 30% or less, more preferably 22% or less, and further preferably 15% or less. When the mass content Wpi exceeds 30%, the resin 2 is poorly impregnated into the base 2 and may be a fiber-reinforced resin with many voids. The mass content Wpi is obtained in accordance with JIS-K7075 (1991) “Test method for fiber content and void ratio of carbon fiber reinforced plastic”.

In the present invention, the volume content Vpi of the continuous porous body of the resin supply material 1 is preferably 0.3% or more, more preferably 0.6% or more, and further preferably 1.0% or more. If the volume content Vpi is less than 0.5%, the amount of the resin is too much for the continuous porous body, and the resin cannot be supported on the continuous porous body, or a large amount of resin flows to the outside during molding. There are things to do. Further, although not particularly limited, the volume content Vpi is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. When the volume content Vpi exceeds 20%, a resin impregnation defect to the base material 2 occurs, and there is a possibility that the fiber reinforced resin has many voids. The volume content Vpi is determined in accordance with JIS-K7075 (1991) “Test method for fiber content and void ratio of carbon fiber reinforced plastic”.

<Base material>
The substrate 2 contained in the preform 3 of the present invention is a fiber substrate made of reinforcing fibers, and is at least one selected from a woven fabric substrate made of reinforcing fibers, a unidirectional substrate, and a mat substrate. It is preferable. Specifically, a fabric base fabric made of continuous fibers, alone or laminated, or a fabric base fabric stitched and integrated with stitch yarn, or a fiber structure such as a three-dimensional fabric or a braid, or a discontinuous fiber A non-woven fabric is preferably used. The continuous fiber means a reinforcing fiber in which the reinforcing fiber bundles are arranged in a continuous state without cutting the reinforcing fiber into a short fiber state. The form and arrangement of the reinforcing fibers used for the substrate 2 in the present invention can be appropriately selected from the forms of continuous fibers such as long fibers, woven fabrics, tows and rovings that are aligned in one direction. The number of filaments in one fiber bundle used for the substrate 2 is preferably 500 or more, more preferably 1500 or more, and further preferably 2500 or more. Further, the number of filaments in one fiber bundle is preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 70000 or less.

For the purpose of obtaining a fiber reinforced resin having high mechanical properties, it is preferable to use a woven fabric base material or a unidirectional base material made of continuous reinforcing fibers for the base material 2. It is preferable to use a mat base material composed of discontinuous fibers as the base material 2 for the purpose of enhancing the properties and obtaining an isotropic fiber reinforced resin.

Moreover, the base material 2 used in the present invention may be a single base material or a laminate of a plurality of base materials, and is a partial laminate depending on the properties required for the preform 3 or fiber reinforced resin. Or what laminated | stacked the different base material may be used.

<Preform>
The preform 3 in the present invention preferably includes a resin supply material 1 and a base material 2, which means a laminated body in which these are arranged or laminated and integrated, from the resin supply material 1 to the base material. From the viewpoint of supplying the resin to 2, it is preferable that the resin supply material 1 and the substrate 2 are adjacent to each other in the thickness direction. Examples of the preform 3 include a sandwich laminate in which the resin supply material 1 or the substrate 2 is sandwiched between the other materials, an alternate laminate in which the resin supply material 1 and the substrate 2 are alternately laminated, and these Combinations are listed. It is preferable to form the preform 3 in advance because the base material 2 can be impregnated with the resin quickly and more uniformly in the manufacturing process of the fiber reinforced resin.

<Method for producing fiber-reinforced resin>
As a manufacturing method of the fiber reinforced resin which supplies and shape | molds resin from the resin supply material 1 to the base material 2 by heating and pressurizing the preform 3 in this invention, the following method is mentioned, for example. That is, a preform 3 including a resin supply material 1 and a base material 2 is produced and set on a mold. Make the resin flowable by the heat of the mold (in the case of a thermosetting resin, the resin viscosity is lowered until the resin is cured, in the case of a thermoplastic resin, it is melted or softened) Resin is supplied to the base material 2 by pressure. The pressing method is preferably press pressure molding or vacuum pressure molding. When the resin is a thermosetting resin, the molding temperature at this time may be the same or different at the time of resin supply and curing. When the resin is a thermoplastic resin, the temperature at the time of resin supply is preferably higher by 10 ° C. than the melting point of the resin. Further, after the resin is supplied, the solidifying temperature is preferably 10 ° C. or more lower than the melting point of the resin, more preferably 30 ° C. or more, and further preferably 50 ° C. or more. The mold used for molding may be a double-sided mold made of a rigid body or a single-sided mold. In the latter case, the preform 3 is placed between the flexible film and the single-sided mold, and the pressure between the flexible film and the single-sided mold is reduced from the outside, so that the preform 3 is added. It becomes a pressed state. When the resin is a thermosetting resin, the thermosetting resin is cured by heating at the time of molding and, if necessary, by further heating to a temperature at which the thermosetting resin is cured after molding. Is obtained. When the resin is a thermoplastic resin, a fiber-reinforced resin can be obtained by cooling and solidifying the molten resin by heating during molding.

〔Example〕
The following examples illustrate the present invention more specifically. First, the evaluation method used in the present invention is described below.

(Evaluation Method 1) Mass mrt per unit area of continuous porous body
Using a continuous porous body, a test piece having a length of 100 mm and a width of 100 mm was cut out and the mass was measured to obtain the mass mrtn (n = 1 to 6) of the continuous porous body. The average value of these and the value calculated from the following formula was defined as the mass mrt per unit area of the continuous porous body.

average value of mrt = mrtn × 100

(Evaluation Method 2) Bending length Crt of continuous porous body at 23 ° C.
Using the continuous porous body, with reference to the bending resistance measurement method defined in JIS-L1913 (2010) “General nonwoven fabric testing method”, the cantilever type testing machine 8 shown in FIG. A test piece having a length of 500 mm was cut out, the front end P of the platform was held down by a 250 g weight 9, and the process of protruding the test piece forward every 10 mm and leaving it for 10 seconds was repeated from the front end P of the platform to 41.5. ° The protruding length when the line drawn below is crossed is read (FIG. 4 (ii)). Half of the read protrusion length was defined as the bending length Crtn (n = 1 to 6), and the average value was defined as the bending length Crt of the continuous porous body.

(Evaluation Method 3) Flexural Grt of Continuous Porous Body at 23 ° C.
The bending length Crt obtained by the evaluation method 2 and the value calculated from the following equation were defined as the bending resistance Grt.

Grt = mrt · Crt ³ × 10 ⁻³
Grt: Bending softness of continuous porous body at 23 ° C. (mN · cm)
mrt: mass per unit area of continuous porous body at 23 ° C. (g / m ² )
Crt: Bending length of continuous porous body at 23 ° C. (cm)

(Evaluation Method 4) Bending length Cmt of continuous porous body at 70 ° C.
The evaluation device used in Evaluation Method 2 was installed in a dryer whose temperature was adjusted so that the internal temperature was 70 ° C., and evaluation was performed in the same manner. At this time, since the inside temperature drops when the door of the dryer is opened and closed and the test piece is operated, the time until the inside temperature returns to 70 ° C. after opening and closing is measured, and the time Observe the positional relationship between the test piece and the line drawn 41.5 ° below the front edge of the platform after 10 seconds. The half length of the read protrusion length was defined as the bending length Cmtn (n = 1 to 6), and the average value was defined as the bending length Cmt of the continuous porous body.

(Evaluation Method 5) Flexibility Gmt of Continuous Porous Body at 70 ° C.
The bending length Cmt obtained by the evaluation method 4 and the value calculated from the following formula were defined as the bending resistance Gmt.

Gmt = mrt · Cmt ³ × 10 ⁻³
Gmt: Bending softness of continuous porous body at 70 ° C. (mN · cm)
mrt: mass per unit area of continuous porous body at 23 ° C. (g / m ² )
Cmt: Bending length of continuous porous body at 70 ° C. (cm)

(Evaluation method 6) Minimum tensile strength σmin of continuous porous body
Using a continuous porous body, a test piece having a width of 50 mm and a length of 280 mm was cut out in directions of + 45 °, 90 °, and −45 ° with a certain direction as a reference of 0 °. Using the obtained test piece, an “Instron” (registered trademark) universal testing machine (manufactured by Instron) was used as a testing machine. In the present invention, the tensile strength refers to a value obtained by dividing the load at the breaking point by the cross-sectional area. The average value of tensile strength in each test piece was σθ (θ = 0, 45, 90, −45). The minimum value at this time was defined as the minimum tensile strength σmin of the continuous porous body.

(Evaluation method 7) Elastic modulus Ert of resin
(In the case of a thermosetting resin) Using a dynamic viscoelasticity measuring device (Rheometer RDA2: manufactured by Rheometrics or Rheometer ARES: manufactured by TA Instruments) as a resin and a tester, a parallel plate having a diameter of 40 mm is used. Resin is arranged, the temperature is simply raised from an initial temperature of 10 ° C. at a rate of temperature increase of 1.5 ° C./min, and the storage elastic modulus G ′ at 23 ° C. when measured at a frequency of 0.5 Hz and Gap 1 mm is the elasticity of the resin. The rate was Ert.

(In the case of thermoplastic resin) After drying the resin under the recommended conditions described in the product catalog (more preferably, drying with a vacuum dryer), an injection molding machine (JSW, J150EII-P) is used. Using this, a Type-I dumbbell test piece conforming to ASTM D638 was molded. The obtained Type-I dumbbell specimen was used, and an “Instron” (registered trademark) universal testing machine (Instron) was used as a testing machine. The value obtained at this time was defined as the elastic modulus Ert of the resin.

(Evaluation method 8) Tensile strength ratio σr of continuous porous body
The minimum tensile strength σmin obtained by the evaluation method 6 and the tensile strength σo in the direction orthogonal to the direction that becomes the minimum tensile strength (when the minimum tensile strength σmin is 0 ° direction, the orthogonal direction is 90 °) Is calculated from the following equation.

σr = σo / σmin

(Evaluation Method 9) Thickness of Continuous Porous Body and Resin Feed Material In accordance with the thickness measurement method specified in JIS-L1913 (2010) “General Nonwoven Testing Method”, the thickness of the continuous porous body and resin feed material Was measured.

(Evaluation Method 10) Handling of Continuous Porous Material, Resin Supply Material, and Preform When preparing each material, the material is wrinkled when it is transported and laminated by grasping the position 2 cm from the end of the material by hand. An assessment was made as to whether it occurred, reworked, or material was torn. The case where it was possible to work without problems was marked as ◯, the case where wrinkles occurred or the work was redone was marked as △, and the case where the material was broken was marked as x.

(Evaluation Method 11) Resin Impregnation Condition of Substrate The obtained fiber reinforced resin was cut out and the cross section was observed with a microscope in the thickness direction to confirm the resin impregnation condition and the presence or absence of voids. The presence or absence of voids in the substrate was determined by the presence or absence of voids having a diameter of 5 μm or more in the observation image of the microscope. The case where the impregnation was sufficiently carried out and no void was found was marked as “◯”, and the case where the impregnation was insufficient or there was a void was marked as “X”.

(Evaluation Method 12) Mechanical Properties of Fiber Reinforced Resin According to JIS-K7074 (1988) “Bending test method of carbon fiber reinforced plastic”, a test piece was cut out from the obtained fiber reinforced resin, and the flexural modulus was obtained.

<Materials used>
In the present invention, since a material having a length of 300 mm and a width of 450 mm is required in the state of the resin supply material, the continuous porous body and the resin were cut out in dimensions of 350 mm and 500 mm in width.

[Continuous porous body (a-1)]
A polyester urethane foam “Mortoprene (registered trademark)” ER-1 manufactured by INOAC Corporation was prepared as a continuous porous body (a-1). The characteristics of this continuous porous body (a-1) are shown in Table 1.

[Continuous porous body (a-2), (a-3)]
Continuous porous bodies (a-2) and (a-3) made of reinforcing fibers were prepared by the following procedure.

(1) Spinning, baking treatment, and surface oxidation treatment were performed from a copolymer containing PAN as a main component to obtain continuous fibers (c-1) having a total number of 12,000 single fibers. The characteristics of this continuous fiber (c-1) were as follows.

Single fiber diameter: 7μm
Mass per unit length: 0.8 g / m
Density: 1.8 g / cm ³
Tensile strength: 4600 MPa
Tensile modulus: 220 GPa

(2) The continuous fiber (c-1) obtained in (1) was cut into a length of 6 mm with a cartridge cutter to obtain a chopped fiber. A dispersion liquid having a concentration of 0.1% by mass composed of water and a surfactant (polyoxyethylene lauryl ether (trade name), manufactured by Nacalai Tex Co., Ltd.) is prepared, and using this dispersion liquid and the chopped fiber, A papermaking substrate was produced with a papermaking substrate production apparatus. The manufacturing apparatus includes a cylindrical container having a diameter of 1000 mm having an opening cock at the bottom of the container as a dispersion tank, and a linear transport section (inclination angle of 30 degrees) that connects the dispersion tank and the papermaking tank. A stirrer is attached to the opening on the upper surface of the dispersion tank, and chopped fiber and dispersion liquid (dispersion medium) can be introduced from the opening. The papermaking tank is a tank provided with a mesh conveyor having a papermaking surface having a width of 500 mm at the bottom, and a conveyor capable of conveying a fiber base material (papermaking base material) is connected to the mesh conveyor. The mass per unit area of the papermaking was adjusted by adjusting the fiber concentration in the dispersion. About 5% by mass of a polyvinyl alcohol aqueous solution (Kuraray Poval, Kuraray Co., Ltd.) as a binder is attached to the paper base made of paper and dried in a drying furnace at 140 ° C. for 1 hour to obtain the desired continuous porous body (a-2) , (A-3) was obtained. The average fiber length of the continuous porous bodies (a-2) and (a-3) was 5.8 mm. The characteristics of these continuous porous bodies (a-2) and (a-3) are as shown in Table 1.

[Continuous porous body (a-4)]
A continuous porous body (a-4) made of reinforcing fibers was prepared by the following procedure.

The continuous fiber (c-1) was cut to a length of 25 mm with a cartridge cutter to obtain a chopped fiber. The obtained chopped fiber was put into a cotton opening machine to obtain a cotton-like fiber aggregate. This fiber assembly is intentionally discontinuous by a carding device having a cylinder roll having a diameter of 600 mm (the rotation speed of the cylinder roll is 320 rpm and the doffer speed is 13 m / min), and the fiber direction is intentionally taken up by the carding device. A continuous porous body (a-4) composed of fibers was obtained. The characteristics of this continuous porous body (a-4) are as shown in Table 1.

[Continuous porous body (a-5)]
“Achilles Board (registered trademark)” manufactured by Achilles Co., Ltd. was prepared as a continuous porous body (a-5). In order to adjust the thickness, the slicer was processed to a thickness of 1.5 mm. The characteristics of this continuous porous body (a-5) are as shown in Table 1.

[Resin (b-1)]
40 parts by mass of “jER” (registered trademark) 1007 (manufactured by Mitsubishi Chemical Corporation), 20 parts by mass of “jER” (registered trademark) 630 (manufactured by Mitsubishi Chemical Corporation), and “Epiclon” (registered trademark) 830 40 parts by mass (manufactured by DIC Corporation), and DICY7 (manufactured by Mitsubishi Chemical Corporation) as a curing agent, an amount that gives 0.9 equivalent of active hydrogen groups to the epoxy groups of all epoxy resin components, a curing accelerator A resin was prepared using 2 parts by mass of DCMU99 (Hodogaya Chemical Co., Ltd.). The prepared resin and a reverse roll coater were used to apply onto a release paper, and film-like resins having masses per unit area of 50 g / m ² and 100 g / m ² were produced. At this time, the mass per unit area of the resin was changed by laminating these resin films according to the purpose. The properties of this resin (b-1) are shown in Table 2.

[Resin (b-2)]
Unmodified polypropylene resin (Prime Polymer Co., Ltd., “Prime Polypro” (registered trademark)) J707G90% by mass; Acid-modified polypropylene resin (Mitsui Chemicals, Inc., “Admer” (registered trademark) QB510) 10% by mass A film-like resin (b-2) having a basis weight of 100 g / m ² was produced using a master batch consisting of The properties of this resin (b-2) are as shown in Table 2.

[Resin supply material (A-1)]
The continuous porous body (a-1) and the resin (b-1) of 750 g / m ² are made to be resin (b-1) / continuous porous body (a-1) / resin (b-1). In a press machine that was laminated and temperature-controlled at 70 ° C., it was heated under a pressure of 0.1 MPa for 1.5 hours to obtain a resin supply material (A-1). The volume content Vpi of the continuous porous body (a-1) of the resin supply material (A-1) was 9.7%, and the mass content Wpi was 10.4%. Other characteristics are as shown in Table 3.

[Resin supply material (A-2)]
A resin supply material (A-2) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-2) was used. The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-2) was 4.3%, and the mass content Wpi was 6.3%. Other characteristics are as shown in Table 3.

[Resin supply material (A-3)]
A resin supply material (A-3) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-3) was used. The volume content Vpi of the continuous porous body (a-3) of the resin supply material (A-3) was 11.9%, and the mass content Wpi was 16.7%. Other characteristics are as shown in Table 3.

[Resin supply material (A-4)]
The continuous porous body (a-2) and the resin (b-2) of 750 g / m ² are made to be resin (b-2) / continuous porous body (a-2) / resin (b-2). In a press machine that is laminated and temperature-controlled at 180 ° C., it is heated for 10 minutes under a pressure of 0.1 MPa, and is cooled until the temperature of the press machine reaches 100 ° C. in the pressurized state. -4) was obtained. The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-4) was 3.3%, and the mass content Wpi was 6.3%. Other characteristics are as shown in Table 3.

[Resin supply material (A-5)]
A resin supply material (A-5) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-4) was used. The volume content Vpi of the continuous porous body (a-4) of this resin supply material (A-5) was 5.8%, and the mass content Wpi was 6.3%. Other characteristics are as shown in Table 3.

[Resin supply material (A-6)]
A resin supply material (A-6) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-5) was used. The continuous porous body (a-5) of the resin supply material (A-6) had a volume content Vpi of 13.6% and a mass content Wpi of 14.5%. Other characteristics are as shown in Table 3.

[Base material (B-1)]
“Torayca” cloth manufactured by Toray Industries, Inc., CO6343B (plain weave, fiber weight 198 g / m ² ) was used as the base material (B-1).

Example 1
300 mm long and 450 mm wide resin supply material (A-1) and base material (B-1), base material (B-1) / base material (B-1) / resin supply material (A-1) / base Lamination was performed such that the material (B-1) / the base material (B-1) was obtained, and a preform (D-1) was obtained. This preform (D-1) was molded by the following molding method to obtain a fiber reinforced resin (E-1).

(1) Using a press machine, pre-form (D-1) is preheated for 10 minutes at 70 ° C. with a surface pressure of 0.
(2) Pressurization is performed at a surface pressure of 1 MPa.
(3) After heating up to 150 ° C. at 3 ° C./min, hold for 40 minutes to cure the resin.

The properties of the fiber reinforced resin (E-1) obtained are as shown in Table 4.

(Example 2)
A preform (D-2) and a fiber reinforced resin (E-2) were obtained in the same manner as in Example 1 except that the resin supply material (A-2) was used. The properties of the obtained fiber reinforced resin (E-2) are as shown in Table 4.

(Example 3)
A preform (D-3) and a fiber reinforced resin (E-3) were obtained in the same manner as in Example 1 except that the resin supply material (A-3) was used. Table 4 shows the properties of the obtained fiber reinforced resin (E-3).

Example 4
Using two resin supply materials (A-2) and four base materials (B-1) as in Example 3, resin supply material (A-2) / base material (B-1) / base material (B-1) / Substrate (B-1) / Substrate (B-1) / Resin feed material (A-2) were laminated to obtain a preform (D-4). A fiber reinforced resin (E-4) was obtained in the same manner as in Example 1 except that the preform (D-4) was used. Table 4 shows the properties of the obtained fiber reinforced resin (E-4).

(Example 5)
Resin supply material (A-4) and base material (B-1), base material (B-1) / base material (B-1) / resin supply material (A-4) / base material (B-1) / Laminated so as to be the base material (B-1) to obtain a preform (D-5). This preform (D-5) was molded by the following molding method to obtain a fiber reinforced resin (E-5).

(1) Using a press machine, the preform (D-5) is preheated at 180 ° C. for 5 minutes with a surface pressure of 0.
(2) Pressurize for 5 minutes at a surface pressure of 1 MPa.
(3) While maintaining the pressurized state of (2), the temperature is lowered to 100 ° C. to solidify the resin.

Properties of the obtained fiber reinforced resin (E-5) are as shown in Table 4.

(Example 6)
The preform (D-2) used in Example 2 was placed on a metal plate, covered with a film from above, and the space between the metal plate and the film was sealed with a sealing material, and the space covered with the film was vacuumed A vacuum state (10 ⁻¹ Pa) was established using a pump. While maintaining this state, it was put in a dryer whose temperature in the cabinet was adjusted to 70 ° C. and preheated for 10 minutes. After preheating, the temperature was raised to 150 ° C. at 3 ° C./min and then held for 40 minutes to cure the resin and obtain a fiber reinforced resin (E-6). Properties of the obtained fiber reinforced resin (E-6) are as shown in Table 4.

In Examples 1 to 4, the continuous porous body, the resin supply material, and the preform could be easily produced. In Example 5, by using a thermoplastic resin in a solidified state at 23 ° C. as a resin, a material with higher handleability and workability was obtained. In Example 6, it was confirmed that the material was suitable for a molding method capable of molding a low-pressure, complex shape such as vacuum pressure molding in accordance with the handleability at 23 ° C. Moreover, by using these materials, it was possible to easily produce a fiber reinforced resin without using an extra auxiliary material.

(Comparative Example 1)
Example 1 was repeated except that only the resin (b-1) was used instead of the resin supply material. Because it is only resin (b-1) (that is, because a continuous porous body is not used), it takes time for the lamination work, such as tearing of the resin film when transported for lamination, and there are many films. The trap of The obtained fiber reinforced resin has more outflow in the in-plane direction than the resin (b-1) impregnated in the base material (B-1), and there are unimpregnated portions. Couldn't get anything.

(Comparative Example 2)
The procedure was the same as Example 1 except that the resin supply material (A-5) was used. At the stage of producing the resin supply material (A-5), the continuous porous body (a-4) was torn and it was difficult to produce a homogeneous resin supply material (A-5). Further, although not as much as Comparative Example 1, it was necessary to handle the layers carefully, and it took a long time for the layering operation. Also, the continuous porous body (a-4) flows out in the in-plane direction due to the pressure during molding, and the resin is not sufficiently supplied to the base material (B-1). Couldn't get anything.

(Comparative Example 3)
The procedure was the same as Example 1 except that the resin supply material (A-6) was used. At the stage of producing the resin supply material (A-6), the resin cannot be impregnated to the center of the continuous porous body (a-5), and both surfaces are resin-rich resin supply material (A-6) It became. It is presumed that this is because the bubbles are independent independent foams and the thickness changes like a sponge due to pressure, and the resin cannot be absorbed (supported). Further, the continuous porous body (a-5) is crushed by the pressure at the time of molding, and the obtained fiber reinforced resin is divided into two separated fibers with the inside of the layer of the continuous porous body (a-5) as a boundary. It became reinforced resin.

[Second embodiment]
The present invention is a resin supply material comprising a continuous porous body and a resin. Moreover, as shown in FIG. 1, this invention is the manufacturing method of the fiber reinforced resin using the preform 3 containing this resin supply material 1 and the base material 2, and the preform 3. As shown in FIG. First, each constituent material will be described.

<Continuous porous body>
The continuous porous body in the present invention requires the tensile strength σrt of the continuous porous body at 23 ° C. to be 0.5 MPa or more for the purpose of expressing the handleability of the resin supply material 1, and It is necessary that the tensile strength ratio σr to be 0.5 or more.

The tensile strength σrt of the continuous porous body at 23 ° C. is that of the continuous porous body when evaluated in accordance with the tensile strength measurement method defined in JIS-L1913 (2010) “General Nonwoven Testing Method”. This is one index indicating the mechanical characteristics, and details will be described later. The “tensile strength ratio” referred to here is the ratio of the tensile strength σmt at 130 ° C. to the tensile strength σrt at 23 ° C., and can be expressed by the following equation.

σr = σmt / σrt

In the present invention, the continuous porous body needs to have a tensile strength σrt of 0.5 MPa or more. For example, both ends of the continuous porous body 5 are held by clamps 7 as shown in FIG. From the viewpoint of preventing breakage due to tension or dead weight during transportation (Fig. 3 (iii)), it is more preferably 1 MPa or more, and further preferably 3 MPa or more. By using such a material, it is possible to apply a high tension when gripping, and in the preform 3 including the resin supply material 1, it is possible to dispose a large number of base materials 2. The degree of freedom can be increased.

On the other hand, the tensile strength σmt at 130 ° C. represents the mechanical properties of the continuous porous body at the time of molding the preform 3 including the resin supply material 1 and the base material 2, and the tensile strength ratio σr (= (σmt / σrt) needs to be 0.5 or more. By using the resin supply material 1 made of such a continuous porous body and a resin, the properties required for obtaining a fiber-reinforced resin having high handling properties during transportation and lamination and high mechanical properties by molding. It is possible to provide the resin supply material 1 in which both are satisfied.

The tensile strength ratio σrtr (= σrt / σrtmax) between the tensile strength σrt of the continuous porous body and the maximum tensile strength σrtmax of the continuous porous body is preferably in the range of 0.8 to 1. By making such a continuous porous body, it is not necessary to consider the direction of the material during lamination, the degree of design freedom and productivity can be improved, and the resulting fiber reinforced resin exhibits isotropic mechanical properties Is possible. At this time, the tensile strength ratio σrtr is more preferably in the range of 0.9 to 1, and further preferably in the range of 0.95 to 1.
The elastic magnification Eb of the continuous porous body in the present invention is preferably in the range of 0.8 to 1. The “elastic magnification” as used herein refers to a restoring force when the continuous porous body is crushed, and details will be described later. From the viewpoint of obtaining a fiber reinforced resin exhibiting high mechanical properties, it is more preferably in the range of 0.9 to 1, and still more preferably in the range of 0.95 to 1. In addition, by making it within such a range, in the step of supporting the resin on the continuous porous body, when the continuous porous body returns from the crushed state to the original thickness, the resin is sucked in like a sponge. It is preferable because the resin flows into the continuous porous body and more resin can be supported. When the elastic magnification Eb is less than 0.8, the continuous porous body is crushed when the pressure is applied in the step of supporting the resin and the step of molding using the preform, the original structure cannot be maintained, and is high. A fiber reinforced resin exhibiting mechanical properties may not be obtained.

The continuous porous body in the present invention is not particularly limited, but it is preferable that the continuous porous body is not melted or softened in the step of obtaining the resin supply material 1, the preform 3, and the fiber reinforced resin. By using such a continuous porous body, it exists in the fiber reinforced resin as a reinforcing material while taking advantage of the characteristics of the continuous porous body having high mechanical properties. Obtainable.

It is preferable that the fibers of the continuous porous body formed by the reinforcing fibers preferably used in the present invention are bonded with a binder. Thereby, handling property, productivity, and workability are improved, and the network structure of the continuous porous body can be maintained. The binder is not particularly limited, but polyvinyl alcohol, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polycarbonate resin, styrene resin, polyamide resin, polyester. Resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polypropylene resin, polyethylene resin, fluororesin, thermoplastic acrylic resin, thermoplastic polyester resin, thermoplastic polyamideimide resin, acrylonitrile-butadiene copolymer Polymers such as polymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, urethane resins, melamine resins, urea resins, thermosetting type Le resins, phenol resins, epoxy resins, thermosetting resins such as thermosetting polyesters is preferably used. From the viewpoint of the mechanical properties of the resulting fiber reinforced resin, at least one function selected from an epoxy group, a hydroxyl group, an acrylate group, a methacrylate group, an amide group, a carboxyl group, a carboxylic acid, an acid anhydride group, an amino group, and an imine group A resin having a group is preferably used. These binders may be used alone or in combination of two or more. The adhesion amount of the binder is preferably 0.01% or more, more preferably 0.1% or more, and further preferably 1% or more. Further, the adhesion amount of the binder is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. If the adhesion amount of the binder exceeds 20%, the drying process may take time or the resin impregnation property may be lowered. On the other hand, when the adhesion amount of the binder is less than 0.01%, when a web made of reinforcing fibers is used for the continuous porous body in the present invention, it is difficult to maintain its form and the handling property may be deteriorated. In addition, the adhesion amount of a binder can be measured by a mass difference before and after the binder application or a baking method.

<Resin>
Although it does not specifically limit as a kind of resin used for this invention, Either a thermosetting resin or a thermoplastic resin can be used. As the thermosetting resin, at least one selected from epoxy resin, vinyl ester resin, phenol resin, thermosetting polyimide resin, polyurethane resin, urea resin, melamine resin, and bismaleimide resin is preferably used. In addition to a single epoxy resin, a copolymer of epoxy resin and a thermosetting resin, a modified product, and a resin blended with two or more types can also be used. As thermoplastic resins, polypropylene, polyethylene, polycarbonate, polyamide, polyester, polyarylene sulfide, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether sulfone, polyimide, polyamide imide, polyether imide, At least one selected from polysulfone is preferably used, and a cyclic oligomer that is a precursor of any of these resins is also preferably used.

The elastic modulus at 23 ° C. of the resin in the present invention is not particularly limited, but is preferably 1 MPa or more, and more preferably 3 MPa or more from the viewpoint of improving handleability and mechanical properties of the fiber reinforced resin, More preferably, it is 5 MPa or more. For example, when the resin is a thermosetting resin, the resin is placed on a parallel plate having a diameter of 40 mm using a dynamic viscoelasticity measuring apparatus as a tester, and the temperature rising rate is 1. It can be evaluated using a storage elastic modulus G ′ at 23 ° C. when the temperature is simply raised at 5 ° C./min and measurement is performed at a frequency of 0.5 Hz and a gap of 1 mm. In addition, when the resin is a thermoplastic resin, after the resin is dried under the recommended conditions described in the product catalog (more preferably, it is dried with a vacuum dryer), an injection molding machine is used in accordance with ASTM D638. A Type-I dumbbell test piece can be molded using an “Instron” (registered trademark) universal testing machine (manufactured by Instron) as a testing machine.

Further, the resin has good handleability at 23 ° C., and is preferably soft and easy to mold at the time of molding and molding, and its elastic modulus is lower than that at 23 ° C. by heating at the time of molding and molding. Those are preferred.

<Resin supply material>
The resin supply material 1 according to the present invention is excellent in transportability in the state of the preform 3 including only the resin supply material 1 or the base material 2, handling property at the time of lamination and moldability at the time of molding, and fiber reinforcement. It is necessary to carry a resin to be a matrix resin of the conductive resin and supply the resin to the base material 2 at the time of molding. Moreover, 0.03 or more is preferable, as for the resin mass change rate P of the resin supply material 1 before and behind shaping | molding represented by following Formula, 0.05 or more is more preferable, and 0.08 or more is further more preferable. Further, in order to obtain a fiber reinforced resin with less voids due to the resin flowing from the resin supply material 1 to the base material 2, the change rate P is preferably 0.99 or less, more preferably 0.7 or less, and 5 or less is more preferable. The resin mass Wr1 in the resin supply material 1 before molding and the resin mass Wr2 in the resin supply material 1 after molding are JIS-K7075 (1991) “Fiber content rate and void ratio test method of carbon fiber reinforced plastic”. Required in compliance with In the case of the preform 3 containing the resin supply material 1, only the resin supply material 1 is taken out by polishing or cutting, and JIS-K7075 (1991) “Testing method for fiber content and void ratio of carbon fiber reinforced plastic” It can also be determined according to

In addition, in order to form a fiber reinforced resin with less voids by the resin flowing (impregnated) from the resin supply material 1 to the base material 2, the continuous porous material in the resin supply material 1 before and after molding represented by the following formula: The volume content change rate Q of the body is preferably 1.1 or more, more preferably 1.3 or more, and even more preferably 1.5 or more. Further, the rate of change Q is preferably 30 or less, more preferably 15 or less, and even more preferably 5 or less so that the resin does not flow out as much as possible and flows efficiently from the resin supply material 1 to the base material 2. The volume content Vpt of the continuous porous body after molding is determined in accordance with JIS-K7075 (1991) “Test method for fiber content and void ratio of carbon fiber reinforced plastic”. Further, instead of the method for specifying the volume content Vpt, the thickness T (unit: mm, measured value), the basis weight Faw (unit: g / m ² , catalog or measured value) of the continuous porous body, and the continuous porosity The volume content Vpt may be obtained by the following formula using the density ρ (unit: g / cm ³ , catalog or measured value) of the material. The thickness T is obtained from the average thickness of any 10 points in the range of 50 mm length and 50 mm width of the resin supply material 1. The thickness direction is a direction orthogonal to the contact surface with the base material 2 used for the preform.

The resin supply material 1 in the present invention is preferably in the form of a sheet, and the sheet thickness at that time is preferably 0.5 mm or more, more preferably 1 mm or more from the viewpoints of handleability, resin supply properties, and mechanical properties. More preferably, it is 1.5 mm or more. Further, from the viewpoint of design freedom and formability, the sheet thickness is preferably 100 mm or less, more preferably 60 mm or less, and even more preferably 30 mm or less.

In the present invention, the mass content Wpi of the continuous porous body of the resin supply material 1 is preferably 0.5% or more, more preferably 1.0% or more, and further preferably 1.5% or more. If the mass content Wpi is less than 0.5%, the amount of the resin is too much for the continuous porous body, and the resin cannot be supported on the continuous porous body, or a large amount of resin flows to the outside during molding. There are things to do. Although not particularly limited, the mass content Wpi is preferably 30% or less, more preferably 22% or less, and further preferably 15% or less. When the mass content Wpi exceeds 30%, the resin 2 is poorly impregnated into the base 2 and may be a fiber-reinforced resin with many voids. The mass content Wpi is obtained in accordance with JIS-K7075 (1991) “Test method for fiber content and void ratio of carbon fiber reinforced plastic”.

<Preform>
The preform 3 in the present invention preferably includes a resin supply material 1 and a base material 2, which means a laminated body in which these are arranged or laminated and integrated, from the resin supply material 1 to the base material. From the viewpoint of supplying the resin to 2, it is preferable that the resin supply material 1 and the substrate 2 are adjacent to each other in the thickness direction. Examples of the preform 3 include a sandwich laminate in which the resin supply material 1 or the substrate 2 is sandwiched between the other materials, an alternate laminate in which the resin supply material 1 and the substrate 2 are alternately laminated, and these Combinations are listed. It is preferable to form the preform in advance because the base material 2 can be impregnated with the resin quickly and more uniformly in the production process of the fiber reinforced resin.

<Method for producing fiber-reinforced resin>
As a manufacturing method of the fiber reinforced resin which supplies and shape | molds resin from the resin supply material 1 to the base material 2 by heating and pressurizing the preform 3 in this invention, the following method is mentioned, for example. That is, a preform including the resin supply material 1 and the substrate 2 is produced and set on a mold. Make the resin flowable by the heat of the mold (in the case of a thermosetting resin, the resin viscosity is lowered until the resin is cured, in the case of a thermoplastic resin, it is melted or softened) Resin is supplied to the base material 2 by pressure. The pressing method is preferably press pressure molding or vacuum pressure molding. When the resin is a thermosetting resin, the molding temperature at this time may be the same or different at the time of resin supply and curing. When the resin is a thermoplastic resin, the temperature at the time of resin supply is preferably higher by 10 ° C. than the melting point of the resin. Further, after the resin is supplied, the solidifying temperature is preferably 10 ° C. or more lower than the melting point of the resin, more preferably 30 ° C. or more, and further preferably 50 ° C. or more. The mold used for molding may be a double-sided mold made of a rigid body or a single-sided mold. In the latter case, the preform 3 is placed between the flexible film and the single-sided mold, and the pressure between the flexible film and the single-sided mold is reduced from the outside, so that the preform 3 is added. It becomes a pressed state. When the resin is a thermosetting resin, the thermosetting resin is cured by heating at the time of molding and, if necessary, by further heating to a temperature at which the thermosetting resin is cured after molding. Is obtained. When the resin is a thermoplastic resin, a fiber-reinforced resin can be obtained by cooling and solidifying the molten resin by heating during molding.

Further, in the present invention, the melting point or softening point of the continuous porous body is preferably higher than the molding temperature, and by using such a molding temperature, the reinforcing material can be used while taking advantage of the high mechanical properties of the continuous porous body. Since a continuous porous body can be present in the fiber reinforced resin, a fiber reinforced resin having high mechanical properties can be obtained. At this time, it is preferable that melting | fusing point or softening point of a continuous porous body is 10 degreeC or more higher than molding temperature, It is more preferable that it is 30 degreeC or more, It is further more preferable that it is 50 degreeC or more higher. The melting point of the resin is a value measured by DSC at a heating rate of 10 ° C./min in accordance with JIS-K7121 (2012). The softening point is a value obtained by measuring the Picad softening temperature in accordance with JIS-K7206 (1999).

(Evaluation Method 1) Tensile strength σrt and maximum tensile strength σrtmax of the continuous porous body.
Using a continuous porous material, a test piece having a width of 50 mm and a length of 280 mm was cut out in the + 45 °, 90 °, and −45 ° directions with a certain direction as a reference of 0 °, and JIS-L1913 (2010) “General nonwoven fabric” The tensile strength was evaluated in accordance with the tensile strength measurement method specified in “Test Method”. As a testing machine, an “Instron” (registered trademark) universal testing machine (manufactured by Instron) was used. In the present invention, the tensile strength refers to a value obtained by dividing the load at the breaking point by the cross-sectional area. The average value of tensile strength in each test piece was σθ (θ = 0, 45, 90, −45). The lowest value at this time was defined as the tensile strength σrt of the continuous porous body. Further, the maximum value at this time was defined as the maximum tensile strength σrtmax of the continuous porous body.

(Evaluation method 2) Tensile strength σmt of continuous porous body at 130 ° C
Using the test piece in the same direction as the tensile strength σrt obtained by the evaluation method 1, the same tensile evaluation as in the evaluation method 1 was performed in a chamber whose temperature was adjusted to 130 ° C. The tensile strength at this time was taken as the tensile strength σmt at 130 ° C.

(Evaluation method 3) Tensile strength ratio σr of continuous porous body
The tensile strength σrt obtained by the evaluation method 1, the tensile strength σmt at 130 ° C. obtained by the evaluation method 2 and the value calculated from the following formula were used as the tensile strength ratio σr of the continuous porous body.

σr = σmt / σrt

(Evaluation Method 4) Tensile Strength Ratio σrtr of Continuous Porous Body at 23 ° C.
The tensile strength σrt and maximum tensile strength σrtmax obtained by the evaluation method 1 and the value calculated from the following formula were used as the tensile strength ratio σrtr of the continuous porous body at 23 ° C.

σrtr = σrt / σrtmax

(Evaluation Method 5) Thickness of Continuous Porous Body and Resin Feed Material In accordance with the thickness measurement method specified in JIS-L1913 (2010) “General Nonwoven Test Method”, the thickness of the continuous porous body and resin feed material Was measured.

(Evaluation Method 6) Elastic magnification Eb of continuous porous body
Using a continuous porous body, a test piece having a length of 50 mm and a width of 50 mm was cut out, and the thickness tb was measured using Evaluation Method 5. As the tester, an “Instron” (registered trademark) universal tester (manufactured by Instron) was used, and a cylindrical indenter having a diameter of φ100 mm and a flat bottom was used. First, the continuous porous body was pressed and crushed to a thickness of 50% of the thickness tb, and the state was maintained for 1 minute. Thereafter, the thickness ta after 3 minutes from releasing the pressure was measured according to the evaluation method 5. The elastic magnification Eb of the continuous porous body was calculated from these thicknesses tb and ta and the following equation.

Eb = ta / tb
tb: thickness of continuous porous body ta: thickness of continuous porous body after pressure crushing

(Evaluation Method 7) Handling of Continuous Porous Material, Resin Supply Material, and Preform When preparing each material, the material is wrinkled when it is transported and laminated by grasping the position 2 cm from the end of the material by hand. An assessment was made as to whether it occurred, reworked, or material was torn. The case where it was possible to work without problems was marked as ◯, the case where wrinkles occurred or the work was redone was marked as △, and the case where the material was broken was marked as x.

(Evaluation Method 8) Resin Impregnation Condition of Substrate The obtained fiber reinforced resin was cut out, and the cross section was observed with a microscope in the thickness direction to confirm the resin impregnation condition and the presence or absence of voids. The presence or absence of voids in the substrate was determined by the presence or absence of voids having a diameter of 5 μm or more in the observation image of the microscope. The case where the impregnation was sufficiently carried out and no void was found was marked as “◯”, and the case where the impregnation was insufficient or there was a void was marked as “X”.

(Evaluation Method 9) Mechanical Properties of Fiber Reinforced Resin According to JIS-K7074 (1988) “Bending test method of carbon fiber reinforced plastic”, a test piece was cut out from the obtained fiber reinforced resin, and the flexural modulus was obtained.

[Continuous porous body (a-1)]
A PPS resin nonwoven fabric made of PPS resin produced by a melt blow method was prepared as a continuous porous body (a-1).

(2) The continuous fiber (c-1) obtained in (1) was cut into a length of 6 mm with a cartridge cutter to obtain a chopped fiber. A dispersion liquid having a concentration of 0.1% by mass composed of water and a surfactant (polyoxyethylene lauryl ether (trade name), manufactured by Nacalai Tex Co., Ltd.) is prepared, and using this dispersion liquid and the chopped fiber, A papermaking substrate was produced with a papermaking substrate production apparatus. The manufacturing apparatus includes a cylindrical container having a diameter of 1000 mm having an opening cock at the bottom of the container as a dispersion tank, and a linear transport section (inclination angle of 30 degrees) that connects the dispersion tank and the papermaking tank. A stirrer is attached to the opening on the upper surface of the dispersion tank, and chopped fiber and dispersion liquid (dispersion medium) can be introduced from the opening. The papermaking tank is a tank provided with a mesh conveyor having a papermaking surface having a width of 500 mm at the bottom, and a conveyor capable of conveying a fiber base material (papermaking base material) is connected to the mesh conveyor. The mass per unit area of the papermaking was adjusted by adjusting the fiber concentration in the dispersion. About 5% by mass of a polyvinyl alcohol aqueous solution (Kuraray Poval, Kuraray Co., Ltd.) as a binder is attached to the paper base made of paper and dried in a drying furnace at 140 ° C. for 1 hour to obtain the desired continuous porous body (a-2) , (A-3) was obtained. The average fiber length of the continuous porous bodies (a-2) and (a-3) was 5.8 mm. The properties of these continuous porous bodies (a-2) and (a-3) are as shown in Table 6.

The continuous fiber (c-1) was cut to a length of 25 mm with a cartridge cutter to obtain a chopped fiber. The obtained chopped fiber was put into a cotton opening machine to obtain a cotton-like fiber aggregate. This fiber assembly is intentionally discontinuous by a carding device having a cylinder roll having a diameter of 600 mm (the rotation speed of the cylinder roll is 320 rpm and the doffer speed is 13 m / min), and the fiber direction is intentionally taken up by the carding device. A continuous porous body (a-4) composed of fibers was obtained. The characteristics of this continuous porous body (a-4) are as shown in Table 6.

[Continuous porous body (a-5)]
“Achilles Board (registered trademark)” manufactured by Achilles Co., Ltd. was prepared as a continuous porous body (a-5). In order to adjust the thickness, the slicer was processed to a thickness of 1.5 mm. The characteristics of this continuous porous material (a-5) are shown in Table 6.

[Continuous porous body (a-6)]
Polyester urethane foam “Mortoprene (registered trademark)” ER-1 manufactured by INOAC CORPORATION was prepared as a continuous porous body (a-6). The characteristics of this continuous porous body (a-6) are shown in Table 6.

[Resin (b-1)]
40 parts by mass of “jER” (registered trademark) 1007 (manufactured by Mitsubishi Chemical Corporation), 20 parts by mass of “jER” (registered trademark) 630 (manufactured by Mitsubishi Chemical Corporation), and “Epiclon” (registered trademark) 830 40 parts by mass (manufactured by DIC Corporation), and DICY7 (manufactured by Mitsubishi Chemical Corporation) as a curing agent, an amount that gives 0.9 equivalent of active hydrogen groups to the epoxy groups of all epoxy resin components, a curing accelerator A resin was prepared using 2 parts by mass of DCMU99 (Hodogaya Chemical Co., Ltd.). The prepared resin and a reverse roll coater were used to apply onto a release paper, and film-like resins having masses per unit area of 50 g / m ² and 100 g / m ² were produced. At this time, the mass per unit area of the resin was changed by laminating these resin films according to the purpose. The properties of this resin (b-1) are shown in Table 7.

[Resin (b-2)]
Unmodified polypropylene resin (Prime Polymer Co., Ltd., “Prime Polypro” (registered trademark)) J707G90% by mass, acid-modified polypropylene resin (Mitsui Chemicals, Inc., “Admer” (registered trademark) QB510) 10% by mass A film-like resin (b-2) having a basis weight of 100 g / m ² was produced using a master batch consisting of The properties of this resin are as shown in Table 7.

[Resin supply material (A-1)]
The continuous porous body (a-1) and the resin (b-1) of 750 g / m ² are made to be resin (b-1) / continuous porous body (a-1) / resin (b-1). In a press machine that was laminated and temperature-controlled at 70 ° C., it was heated under a pressure of 0.1 MPa for 1.5 hours to obtain a resin supply material (A-1). The volume content Vpi of the continuous porous body (a-1) of the resin supply material (A-1) was 6.6%, and the mass content Wpi was 7.4%. Other characteristics are as shown in Table 8.

[Resin supply material (A-2)]
A resin supply material (A-2) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-2) was used. The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-2) was 4.3%, and the mass content Wpi was 6.3%. Other characteristics are as shown in Table 8.

[Resin supply material (A-3)]
A resin supply material (A-3) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-3) was used. The volume content Vpi of the continuous porous body (a-3) of the resin supply material (A-3) was 11.9%, and the mass content Wpi was 16.7%. Other characteristics are as shown in Table 8.

[Resin supply material (A-4)]
The continuous porous body (a-2) and the resin (b-2) of 750 g / m ² are made to be resin (b-2) / continuous porous body (a-2) / resin (b-2). In a press machine that is laminated and temperature-controlled at 180 ° C., it is heated for 10 minutes under a pressure of 0.1 MPa, and is cooled until the temperature of the press machine reaches 100 ° C. in the pressurized state. -4) was obtained. The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-4) was 3.3%, and the mass content Wpi was 6.3%. Other characteristics are as shown in Table 8.

[Resin supply material (A-5)]
A resin supply material (A-5) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-4) was used. The volume content Vpi of the continuous porous body (a-4) of this resin supply material (A-5) was 5.8%, and the mass content Wpi was 6.3%. Other characteristics are as shown in Table 8.

[Resin supply material (A-6)]
A resin supply material (A-6) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-5) was used. The continuous porous body (a-5) of the resin supply material (A-6) had a volume content Vpi of 13.6% and a mass content Wpi of 14.5%. Other characteristics are as shown in Table 8.

[Resin supply material (A-7)]
A resin supply material (A-7) was obtained in the same manner as the resin supply material (A-1) except that the continuous porous body (a-6) was used. The volume content Vpi of the continuous porous body (a-6) of the resin supply material (A-1) was 9.7%, and the mass content Wpi was 10.4%. Other characteristics are as shown in Table 8.

Example 1
300 mm long and 450 mm wide resin supply material (A-1) and base material (B-1), base material (B-1) / base material (B-1) / resin supply material (A-1) / base Lamination was performed such that the material (B-1) / the base material (B-1) was obtained, and a preform (D-1) was obtained. This preform (D-1) was molded by the following molding method to obtain a fiber reinforced resin 1.

(1) Using a press machine, pre-form (D-1) is preheated for 10 minutes at 70 ° C. with a surface pressure of 0.
(2) Pressurization is performed at a surface pressure of 1 MPa.
(3) After heating up to 150 ° C. at 3 ° C./min, hold for 40 minutes to cure.

The properties of the obtained fiber reinforced resin (E-1) are as shown in Table 9.

(Example 2)
A preform (D-2) and a fiber reinforced resin (E-2) were obtained in the same manner as in Example 1 except that the resin supply material (A-2) was used. Table 9 shows the properties of the obtained fiber reinforced resin (E-2).

(Example 3)
A preform (D-3) and a fiber reinforced resin (E-3) were obtained in the same manner as in Example 1 except that the resin supply material (A-3) was used. Table 9 shows the properties of the obtained fiber reinforced resin (E-3).

Example 4
Using two resin supply materials (A-2) and four base materials (B-1) as in Example 3, resin supply material (A-2) / base material (B-1) / base material (B-1) / Substrate (B-1) / Substrate (B-1) / Resin feed material (A-2) were laminated to obtain a preform (D-4). A fiber reinforced resin (E-4) was obtained in the same manner as in Example 1 except that the preform (D-4) was used. Table 9 shows the properties of the obtained fiber reinforced resin (E-4).

Properties of the obtained fiber reinforced resin (E-5) are as shown in Table 9.

(Example 6)
The preform (D-2) used in Example 2 was placed on a metal plate, covered with a film from above, and the space between the metal plate and the film was sealed with a sealing material, and the space covered with the film was vacuumed A vacuum state (10 ⁻¹ Pa) was established using a pump. While maintaining this state, it was put in a dryer whose temperature in the cabinet was adjusted to 70 ° C. and preheated for 10 minutes. After preheating, the temperature was raised to 150 ° C. at 3 ° C./min and then held for 40 minutes to cure the resin and obtain a fiber reinforced resin (E-6). Table 9 shows the properties of the obtained fiber reinforced resin (E-6).

In Examples 1 to 4, the continuous porous body, the resin supply material, and the preform could be easily produced. In Example 5, the thermoplastic resin in a solidified state at 23 ° C. was used as the resin, and thus the material was more handleable and workable. In Example 6, it was confirmed that the material was suitable for a molding method capable of molding a low-pressure, complex shape such as vacuum pressure molding in accordance with the handleability at 23 ° C. Moreover, by using these materials, it was possible to easily produce a fiber reinforced resin without using an extra auxiliary material.

(Comparative Example 4)
A fiber reinforced resin was obtained in the same manner as in Example 1 except that the resin supply material (A-7) was used. The properties of the obtained fiber reinforced resin are as shown in Table 10. The continuous porous body (a-6) constituting the resin supply material (A-7) melts at the stage of molding the preform, and the form of the continuous porous body before molding cannot be maintained, The porous void portion was crushed and became a form similar to a resin sheet, and sufficient mechanical properties could not be expressed.

[Third embodiment]

<Resin supply material>
The resin supply material of the present invention is a resin supply material containing at least a continuous porous body and a resin. As shown in FIG. 1, the resin supply material 1 is prepared by laminating the resin supply material 1 with a base material 2 to produce a preform 3, and heating and pressurizing the preform 3 in a closed space, for example. By supplying the resin from the supply material 1 to the base material 2, it is possible to manufacture a fiber reinforced resin. That is, the resin becomes a matrix resin of the fiber reinforced resin.

Here, the preform 3 means a laminated body in which the resin supply material 1 and the base material 2 are laminated and integrated, and the outermost layer of the laminated body in which a predetermined number of the resin supply materials 1 are laminated and integrated. Can be exemplified by a sandwich laminate in which the substrate 2 is sandwiched, an alternate laminate in which the resin supply material 1 and the substrate 2 are alternately laminated, and a combination thereof. It is preferable to form the preform 3 in advance because the base material 2 can be impregnated with the resin quickly and more uniformly in the manufacturing process of the fiber reinforced resin.

In the method for producing a fiber reinforced resin using the resin supply material 1 of the present invention, it is preferable that the resin can be supplied from the resin supply material 1 to the base material 2 while preventing the mixing of voids as much as possible. It is preferable to use a molding method. The mold to be used may be a double-sided type such as a closed type made of a rigid body or a single-sided type. In the latter case, the preform 3 can be placed between the flexible film and the rigid open mold (in this case, the space between the flexible film and the rigid open mold is in a reduced pressure state from the outside, The preform 3 is in a pressurized state).

<Continuous porous body>
Examples of the form of the continuous porous body include a porous sheet and a fiber substrate such as a unidirectional substrate formed of fibers, a woven substrate, and a web. As a form of a fiber, it is preferable that it is a discontinuous fiber from a viewpoint of resin supply property. As the discontinuous fiber, a bundle shape or a single fiber shape can be exemplified, and a web having voids impregnated with resin between the fibers is preferable. There is no restriction | limiting in the form and shape of a web, For example, dissimilar fiber may be mixed, fiber may be meshed with other components, or the fiber may be adhere | attached with the resin component. From the viewpoint of easily producing a web in which fibers are dispersed, a base material in which fibers are sufficiently opened in a non-woven form obtained by a dry method or a wet method and single fibers are bonded with a binder made of an organic compound. It can be illustrated as a preferred shape.

It is preferable that continuous porous fibers formed of fibers preferably used in the present invention are bonded together with a binder. Thereby, handling property, productivity, and workability are improved, and the network structure of the continuous porous body can be maintained. The binder is not particularly limited, but polyvinyl alcohol, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polycarbonate resin, styrene resin, polyamide resin, polyester. Resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polypropylene resin, polyethylene resin, fluororesin, thermoplastic acrylic resin, thermoplastic polyester resin, thermoplastic polyamideimide resin, acrylonitrile-butadiene copolymer Polymers such as polymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, urethane resins, melamine resins, urea resins, thermosetting type Le resins, phenol resins, epoxy resins, thermosetting resins such as thermosetting polyesters is preferably used. From the viewpoint of the mechanical properties of the resulting fiber reinforced resin, at least one function selected from an epoxy group, a hydroxyl group, an acrylate group, a methacrylate group, an amide group, a carboxyl group, a carboxylic acid, an acid anhydride group, an amino group, and an imine group A resin having a group is preferably used. These binders may be used alone or in combination of two or more. The adhesion amount of the binder is preferably 0.01% or more, more preferably 0.1% or more, and further preferably 1% or more. Further, the adhesion amount of the binder is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. If the adhesion amount of the binder exceeds 20%, the drying process may take time or the resin impregnation property may be lowered. On the other hand, when the adhesion amount of the binder is less than 0.01%, when a web made of fibers is used in the present invention, it is difficult to maintain the form and the handling property may be deteriorated. In addition, the adhesion amount of a binder can be measured by a mass difference before and after the binder application or a baking method.

The average fiber length of the fibers is preferably 0.1 mm or more, more preferably 1 mm or more, and further preferably 2 mm or more. The average fiber length of the fibers is not particularly limited, but is preferably 100 mm or less, more preferably 50 mm or less, and even more preferably 10 mm or less, from the viewpoint of isotropic properties of the continuous porous body and fiber dispersibility. Examples of a method for measuring the average fiber length include, for example, a method in which fibers are directly extracted from a fiber base material and measured by microscopic observation, or a resin is dissolved using a solvent that dissolves only the resin in the resin supply material 1 and remains. There is a method in which the collected fibers are filtered and measured by microscopic observation (dissolution method). In the case where there is no solvent for dissolving the resin, there is a method (burn-off method) in which only the resin is burned out in a temperature range in which the fiber does not lose weight, and the fibers are separated and measured by microscopic observation. The measurement can be performed by randomly selecting 400 fibers, measuring the length with an optical microscope up to 1 μm unit, and measuring the fiber length and its ratio. In addition, when the method of extracting a fiber directly from a fiber base material and the method of extracting a fiber fiber from the resin supply material 1 by a burning method or a dissolution method are compared, the result obtained by selecting conditions appropriately There will be no special difference.

The viscosity at the time of resin impregnation (molding) in the present invention is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less, and even more preferably 10 Pa · s or less. When it exceeds 1000 Pa · s, there is a concern that voids are generated in the obtained fiber-reinforced resin because the base material 2 described later is not sufficiently impregnated with the resin.

In the resin supply material 1 of the present invention, in the first embodiment, the thermal conductivity of the material forming the continuous porous body needs to be 1.2 W / m · K or more, and 5 W / m · K or more. More preferably, it is more preferably 10 W / m · K or more, and particularly preferably 50 W / m · K or more. Further, from the viewpoint of moldability, the thermal conductivity is preferably 1400 W / m or less.

In the first embodiment, when a porous sheet is used as the continuous porous body, for example, a sheet made of a porous material such as porous ceramics or porous silicon is preferably used.

In addition, when using fiber base materials such as unidirectional base materials, woven base materials, and webs formed of fibers as continuous porous bodies, gold, silver, copper, aluminum, nickel, iron, platinum, brass, stainless steel, etc. Metal fibers, polyacrylonitrile (PAN) -based, lignin-based, pitch-based, rayon-based carbon fibers, and inorganic fibers such as silicon carbide and silicon nitride. Moreover, the surface treatment may be given to these fibers.

As for carbon fibers, polyacrylonitrile (PAN) -based and pitch-based carbon fibers are preferably used from the viewpoint of thermal conductivity, and in particular, PAN-based carbon fibers having a strand elastic modulus of 200 GPa or more, more preferably 350 GPa or more, Preference is given to pitch-based carbon fibers having an elastic modulus of 400 GPa or more.

The thermal conductivity of the material constituting the continuous porous body can be measured by the following method. When the form of the continuous porous body is a porous sheet, the thermal diffusivity of the solid body made of the same material is measured by a flash method using a thermal diffusivity measuring device (for example, LFA 447 (Nanoflash) manufactured by NETZSCH). taking measurement. Further, the density of the solid substance was measured by an Archimedes method using an electronic analytical balance (for example, AEL-200 manufactured by Shimadzu Corporation), and the specific heat was further measured by a differential scanning calorimeter (for example, manufactured by Perkin-Elmer). Measured by DSC method using DSC-7). The thermal conductivity (W / m · K) is calculated from the product of the thermal diffusivity, density and specific heat thus measured.

When the form of the continuous porous body is a fiber base material formed of fibers, the thermal diffusivity of the fibers forming the fiber base material is measured using a thermal diffusivity measuring device (for example, LaserPIT manufactured by ULVAC-RIKO Co., Ltd.). Measure with the optical alternating current method. In addition, the density of such fibers is measured by a gas substitution method using a dry automatic densimeter (for example, Accupic 1330-03 manufactured by Micromeritics) and an electronic analysis balance (for example, AFL-200 manufactured by Shimadzu Corporation). Further, the specific heat is measured by a DSC method using a differential scanning calorimeter (for example, DSC-7 manufactured by Perkin-Elmer). The thermal conductivity (W / m · K) is calculated from the product of the thermal diffusivity, density and specific heat thus measured.

For the resin supply material 1 of the present invention, in the second embodiment, it is necessary to include a filler having a thermal conductivity of 1.2 W / m · K or higher, and a filler having a thermal conductivity of 10 W / m · K or higher. It is preferable to include a filler, more preferably 50 W / m · K or more, and still more preferably 200 W / m · K or more. In addition, it is sufficient if the thermal conductivity of the filler is 3000 W / m · K or less.

In the second embodiment, when a porous sheet is used as the continuous porous body, the porous sheet is a porous material such as urethane foam, melamine foam, foamed PP sheet, foamed polyethylene, foamed polystyrene, foamed polyester, etc. Examples thereof include inorganic porous sheets made of a porous material such as organic porous sheets and silicone foam, porous ceramics, porous silicon, and porous glass.

Fillers include metallic fillers such as copper, silver, gold, aluminum and nickel, carbon fillers such as graphite, graphene, carbon black, carbon nanotubes, carbon fibers and ultrafine carbon fibers, boron nitride, aluminum nitride, aluminum oxide, etc. The ceramic type filler can be illustrated.

The number average particle diameter of the filler is preferably 100 μm or less, more preferably 60 μm or less, and particularly preferably 20 μm or less. By setting the average particle diameter of the filler in such a range, the resin may be supplied promptly without hindering the flow of the resin during molding. The number average particle size of the filler is preferably 10 nm or more. By setting it as this range, the cohesive force of a filler is adjusted and the aggregate with which the filler was connected in multiple can be disperse | distributed in resin.

The number average particle diameter of the filler is a value obtained by observing with a field emission scanning electron microscope (FE-SEM), and measuring the average diameter of 60 arbitrary particles after measuring the diameter of the circumscribed circle of the particles as the particle diameter. And

The volume content Vc of the filler with respect to the resin is preferably 1% or more and 30% or less from the balance between the amount of the resin in the resin supply material 1 and the thermal conductivity. In addition, it is preferable that the resin supply material 1 of this invention also contains an above described filler also in a 1st form. That is, the resin supply material 1 of the present invention has more excellent effects by having both the first form and the second form.

In the resin supply material 1 of the present invention, the resin mass change rate P of the resin supply material 1 before and after molding, represented by the following formula, is preferably 0.03 or more, more preferably 0.05 or more, and 0.08 or more. Is more preferable. Further, in order to obtain a fiber reinforced resin with less voids due to the resin flowing from the resin supply material 1 to the base material 2, the change rate P is preferably 0.99 or less, more preferably 0.7 or less, and 5 or less is more preferable. The resin mass Wr2 in the resin supply material 1 after molding can be obtained by a blow-off method by removing only the resin supply material 1 by polishing or cutting.

By using such a resin supply material 1, it becomes possible to supply the resin to a larger amount of the base material 2, and the design flexibility and mechanical characteristics of the fiber reinforced resin can be increased.

The resin supply material 1 of the present invention is preferably composed of a continuous porous body and a resin, and is in the form of a sheet. The sheet thickness is preferably a sheet-like substrate of 0.5 mm or more, more preferably 1 mm or more, and further preferably 1.5 mm or more from the viewpoint of resin supply property and mechanical properties. Further, from the viewpoints of handleability and formability, the sheet thickness is preferably a sheet-like base material of 100 mm or less, more preferably 60 mm or less, and further preferably 30 mm or less.

The mass content Wpi of the continuous porous body of the resin supply material 1 in the present invention is preferably 0.5% or more, more preferably 1.0% or more, and further preferably 1.5% or more. If the mass content Wpi is less than 0.5%, the amount of the resin is too much for the continuous porous body, and the resin cannot be supported on the continuous porous body, or a large amount of resin flows to the outside during molding. There are things to do. Although not particularly limited, the mass content Wpi is preferably 30% or less, more preferably 22% or less, and further preferably 15% or less. When the mass content Wpi exceeds 30%, the resin 2 is poorly impregnated into the base 2 and may be a fiber-reinforced resin with many voids.

The volume content Vpi of the continuous porous body of the resin supply material 1 in the present invention is preferably 0.3% or more, more preferably 0.6% or more, and further preferably 1% or more. If the volume content Vpi is less than 0.5%, the amount of the resin is too much for the continuous porous body, and the resin cannot be supported on the continuous porous body, or a large amount of resin flows to the outside during molding. There are things to do. Further, although not particularly limited, the volume content Vpi is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. When the volume content Vpi exceeds 20%, a resin impregnation defect to the base material 2 occurs, and there is a possibility that the fiber reinforced resin has many voids.

<Base material>
The preform of the present invention includes the resin supply material 1 and the base material 2 described above. Usually, the base material 2 is a state which does not contain matrix resin, ie, a dry state. In the present invention, the substrate 2 used for the preform 3 is a fiber substrate made of reinforcing fibers, and is at least one selected from a woven fabric substrate made of reinforcing fibers, a unidirectional substrate, and a mat substrate. Preferably there is. Specifically, a fabric base fabric made of continuous fibers, alone or laminated, or a fabric base fabric stitched and integrated with stitch yarn, or a fiber structure such as a three-dimensional fabric or a braid, or a discontinuous fiber A non-woven fabric is preferably used. The continuous reinforcing fiber means a carbon fiber in which carbon fiber bundles are arranged in a continuous state without cutting the reinforcing fiber into a short fiber state.

For the purpose of obtaining a fiber reinforced resin having high mechanical properties, it is preferable to use a woven base material or a unidirectional base material made of continuous reinforcing fibers for the base material 1, but the impregnation rate of the thermosetting resin is increased to increase the fiber reinforcement. For the purpose of increasing the productivity of the resin, it is preferable to use a mat substrate made of discontinuous fibers as the substrate 2. Further, the base material 2 used in the present invention may be a single base material or a laminate of a plurality of base materials, and may be a partially laminated material depending on the properties required for the preform or fiber reinforced resin. What laminated | stacked the different base material may be used.

<Method for producing fiber-reinforced resin>
As a method for producing a fiber reinforced resin using the resin supply material 1 of the present invention, for example, a fiber to be molded by supplying the resin from the resin supply material 1 to the substrate 2 by heating and pressurizing the preform 3 described above. The manufacturing method of reinforced resin is mentioned. That is, a preform including the resin supply material 1 and the substrate 2 is produced and set on a mold. Make the resin flowable by the heat of the mold (in the case of a thermosetting resin, the resin viscosity is lowered until the resin is cured, in the case of a thermoplastic resin, it is melted or softened) Resin is supplied to the base material 2 by pressure. The pressing method is preferably press pressure molding or vacuum pressure molding. When the resin is a thermosetting resin, the mold temperature at this time may be the same or different between the resin supply temperature and the curing temperature. When the resin is a thermoplastic resin, the temperature at the time of resin supply is preferably higher by 10 ° C. than the melting point of the resin. Further, after the resin is supplied, the solidifying temperature is preferably 10 ° C. or more lower than the melting point of the resin, more preferably 30 ° C. or more, and further preferably 50 ° C. or more. The mold used for molding may be a double-sided mold made of a rigid body or a single-sided mold. In the latter case, the preform is pressed between the flexible film and the single-sided mold, and the pressure between the flexible film and the single-sided mold is reduced from the outside. It becomes the state. When the resin is a thermosetting resin, the thermosetting resin is cured by heating at the time of molding and, if necessary, by further heating to a temperature at which the thermosetting resin is cured after molding. Is obtained. When the resin is a thermoplastic resin, a fiber-reinforced resin can be obtained by cooling and solidifying the resin melted by heating during molding. Since the resin supply material 1 of the present invention is excellent in thermal conductivity, temperature unevenness generated in the material during molding can be reduced, and it is also suitable for molding thick materials.

〔Example〕
Hereinafter, the present invention will be described more specifically with reference to examples. Further, the present invention is not limited to these examples.

<Evaluation method>
[Measurement of thermal conductivity of fiber]
The thermal diffusivity was an average value when the sample was changed twice under the following conditions by the optical alternating current method.

Measuring device: ULVAC-RIKO thermal diffusivity measuring device LaserPIT
Irradiation light: Semiconductor laser temperature sensor: E thermocouple (wire diameter 100 μm, silver paste attached)
Atmosphere: Measurement temperature in vacuum: 25 ° C
Measurement direction: Fiber axis direction

The density was the average value when the sample was changed twice by the gas replacement method under the following conditions.

Measuring device: Dry automatic densimeter Accupic 1330-03 manufactured by Micromeritics.
Balance: Electronic analysis balance AFL-200 manufactured by Shimadzu Corporation
Measurement temperature: 25 ° C
Filling gas: helium

The specific heat was the average of the values measured twice by changing the sample under the following conditions by the DSC method.

Measuring apparatus: Differential scanning calorimeter DSC-7 manufactured by Perkin-Elmer
Rate of temperature increase: 10 ° C./min Standard sample: Sapphire (α-Al ₂ O ₃ )
Atmosphere: In dry nitrogen stream Sample container: Aluminum container (φ6mm × 1mm)

The thermal conductivity (W / m · K) of the fiber was calculated from the product of the thermal diffusivity, density and specific heat of the fiber.

[Measurement of thermal conductivity of fiber reinforced resin]
Based on ASTM E530, measurement was performed using GH-1S manufactured by ULVAC-RIKO. For the test pieces, four fiber reinforced resins (E-1 to 15) described later were cut out in a size of 20 mm × 3 mm, respectively, and tilted by 90 ° so that the side of 3 mm, that is, the fiber direction was the measurement direction, to become a rectangular parallelepiped 4 What contacted the test piece of the book was used.

[Thickness of resin supply material]
The thickness of the resin feed material was measured in accordance with the thickness measurement method specified in JIS-L1913 (2010) “General Nonwoven Test Method”.

[Impregnation of resin in fiber reinforced resin]
When the resin non-impregnated portion of the surface layer of the molded product was 30% or more, it was determined that molding was impossible (x), and other cases were determined as molding possible (◯). The evaluation results are as shown in Table 11.

<Material>
[fiber]
Fiber (d-1) (carbon fiber)
Spinning, baking treatment and surface oxidation treatment were carried out from a PAN-based copolymer to obtain continuous carbon fibers having a total number of 12,000 single fibers. The characteristics of this continuous carbon fiber were as follows.

Single fiber diameter: 7μm
Mass per unit length: 0.8 g / m
Specific gravity: 1.8
Tensile strength: 4600 MPa
Tensile modulus: 220 GPa
Thermal conductivity: 12.3 W / m · K

Fiber (d-2) (carbon fiber)
Spinning, baking treatment and surface oxidation treatment were carried out from a PAN-based copolymer to obtain continuous carbon fibers having a total number of 12,000 single fibers. The characteristics of this continuous carbon fiber were as follows.

Single fiber diameter: 5 μm
Mass per unit length: 0.5 g / m
Specific gravity: 1.8
Tensile strength: 4400 MPa
Tensile modulus: 380 GPa
Thermal conductivity: 61.3W / m · K

[Filler]
Filler (c-1)
V325F (Ai ₂ O ₃ , manufactured by Nippon Light Metal Co., Ltd., number average particle size 12 μm, Al ₂ O ₃ purity 99.7%, thermal conductivity 30 W / m · K)

Filler (c-2)
UHP-1K (Boron nitride, manufactured by Showa Denko KK, number average particle size 8 μm, boron nitride purity 99.9%, thermal conductivity 60 W / m · K)

Filler (c-3)
FLZ-1 (aluminum nitride, manufactured by Toyo Aluminum Co., Ltd., number average particle size 9.8 μm, thermal conductivity 300 W / m · K)

[resin]
Resin (b-1)
40 parts by mass of “jER (registered trademark)” 1007 (manufactured by Mitsubishi Chemical Corporation), 20 parts by mass of “jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Corporation), “Epiclon (registered trademark)” 830 40 parts by mass (manufactured by DIC Corporation), and DICY7 (manufactured by Mitsubishi Chemical Corporation) as a curing agent, an amount that gives 0.9 equivalent of active hydrogen groups to the epoxy groups of all epoxy resin components, a curing accelerator Resin (b-1) was prepared using 2 parts by mass of DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.).

The obtained resin (b-1) is applied onto release paper using a reverse roll coater to produce resin films (b-1) having masses per unit area of 50 g / m ² and 100 g / m ^2. did. At this time, the mass per unit area of the film was changed by laminating these films according to the purpose.

[Production of filler and resin mixture]
Mixture (1)
The filler (c-1) is added to the resin (b-1) so that the volume content is 6.0%, and heated at 60 ° C. for 2 hours using a hot air dryer, the viscosity of the resin (b-1) Was set as a region suitable for kneading. This mixture was kneaded with a rotation / revolution mixer (manufactured by Shinky Co., Ltd.) at 1600 rpm for 10 minutes to obtain a mixture (1).

The obtained mixture (1) was applied onto release paper using a reverse roll coater to produce a film (1) of a mixture having masses per unit area of 50 g / m ² and 100 g / m ² . At this time, the mass per unit area of the film was changed by laminating these films according to the purpose.

Mixture (2)
The filler (c-2) is added to the resin (b-1) so that the volume content is 7.2%, and heated at 60 ° C. for 2 hours using a hot air dryer, the viscosity of the resin (b-1) Was set as a region suitable for kneading. This mixture was kneaded with a rotation / revolution mixer (manufactured by Shinky Corp.) at 1600 rpm for 10 minutes to obtain a mixture (2).

The obtained mixture (2) was applied onto release paper using a reverse roll coater to produce a film (2) of a mixture having masses per unit area of 50 g / m ² and 100 g / m ² . At this time, the mass per unit area of the film was changed by laminating these films according to the purpose.

Mixture (3)
The filler (c-3) is added to the resin (b-1) so that the volume content is 7.1%, and heated at 60 ° C. for 2 hours using a hot air dryer, the viscosity of the resin (b-1) Was set as a region suitable for kneading. This mixture was kneaded with a rotation / revolution mixer (manufactured by Shinky Co., Ltd.) at 1600 rpm for 10 minutes to obtain a mixture (3).

The obtained mixture (3) was applied onto release paper using a reverse roll coater to produce a film (3) of a mixture having masses per unit area of 50 g / m ² and 100 g / m ² . At this time, the mass per unit area of the film was changed by laminating these films according to the purpose.

[Continuous porous material]
Continuous porous material (a-1)
The fiber (d-1) was cut into a predetermined length with a cartridge cutter to obtain a chopped carbon fiber. A dispersion liquid having a concentration of 0.1% by mass composed of water and a surfactant (polyoxyethylene lauryl ether (trade name), manufactured by Nacalai Tex Co., Ltd.) is prepared, and the dispersion liquid and the chopped carbon fiber are used. Then, a papermaking substrate was produced with a papermaking substrate production apparatus. The manufacturing apparatus includes a cylindrical container having a diameter of 1000 mm having an opening cock at the bottom of the container as a dispersion tank, and a linear transport section (inclination angle of 30 degrees) that connects the dispersion tank and the papermaking tank. A stirrer is attached to the opening on the upper surface of the dispersion tank, and chopped carbon fiber and dispersion liquid (dispersion medium) can be input from the opening. The papermaking tank is a tank provided with a mesh conveyor having a papermaking surface having a width of 500 mm at the bottom, and a conveyor capable of transporting a carbon fiber substrate (papermaking substrate) is connected to the mesh conveyor. Papermaking adjusted the mass per unit area by adjusting the carbon fiber concentration in the dispersion. About 5% by mass of a polyvinyl alcohol aqueous solution (Kuraray Poval, Kuraray Co., Ltd.) as a binder was attached to the paper-made carbon fiber substrate and dried in a drying oven at 140 ° C. for 1 hour to obtain the desired carbon fiber web. The mass per unit area was 100 g / m ² and the average fiber length was 5.8 mm. The web obtained here was used as a continuous porous body (a-1).

Continuous porous material (a-2)
A continuous porous body (a-2) was obtained in the same manner as the continuous porous body (a-1) except that the fiber (d-2) was used.

Continuous porous material (a-3)
FEO-030 (Olivest Co., Ltd. glass fiber web, 30 g / m ² , fiber thermal conductivity 1.0 W / m · K)

[Resin supply materials]
Resin supply material (A-1)
A laminated body (200 g / m ² ) of continuous porous body (a-1) and a resin film (1) of 1300 g / m ² were combined into resin film (1) / continuous porous body (a-1) / resin film ( In a press machine laminated to 1) and adjusted to 70 ° C., it was heated under a pressure of 0.1 MPa for 1.5 hours to obtain a resin supply material (A-1). The volume content Vpi of the continuous porous body (a-1) of the resin supply material (A-1) was 4.9%, the mass content Wpi was 7.1%, and the thickness was 2.3 mm.

Resin supply material (A-2)
A laminated body (200 g / m ² ) of continuous porous body (a-2) and a resin film (1) of 1300 g / m ² are combined into resin film (1) / continuous porous body (a-2) / resin film ( In a press machine laminated to 1) and adjusted to 70 ° C., it was heated for 1.5 hours under a surface pressure of 0.1 MPa to obtain a resin supply material (A-2). The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-2) was 4.9%, the mass content Wpi was 7.1%, and the thickness was 2.3 mm.

Resin supply material (A-3)
Continuous, porous body (a-2) laminate film (200 g / ^{m 2),} and mixtures 1450 g / ^{m 2} (1), a film of the mixture (1) / continuous porous body (a-2) / mixture In a press machine laminated to be film (1) and heated to 70 ° C., it was heated for 1.5 hours under a surface pressure of 0.1 MPa to obtain a resin supply material (A-3). The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-3) was 4.9%, the mass content Wpi was 6.6%, and the thickness was 2.2 mm.

Resin supply material (A-4)
Continuous, porous body (a-2) laminate film (200 g / ^{m 2),} and mixtures 1450 g / ^{m 2} (2), the film (2) / continuous porous body of the mixture (a-2) / mixture In a press machine laminated to be film (2) and heated to 70 ° C., it was heated for 1.5 hours under a surface pressure of 0.1 MPa to obtain a resin supply material (A-4). The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-4) was 4.9%, the mass content Wpi was 6.4%, and the thickness was 2.3 mm.

Resin supply material (A-5)
Continuous, porous body (a-2) laminate (200 g / ^{m 2)} and of a mixture of 1450 g / ^{m 2} film (3), the film (3) / continuous porous body of the mixture (a-2) / mixture In a press machine which was laminated so as to be a film (3) of which the temperature was adjusted to 70 ° C., it was heated for 1.5 hours under a surface pressure of 0.1 MPa to obtain a resin supply material (A-5). The volume content Vpi of the continuous porous body (a-2) of the resin supply material (A-5) was 4.9%, the mass content Wpi was 6.5%, and the thickness was 2.3 mm.

Resin supply material (A-6)
Continuous, porous body (a-3) laminate film (300 g / ^{m 2),} and mixtures 1450 g / ^{m 2} (1), film (1) / continuous porous body of the mixture (a-3) / mixture In a press machine which was laminated so as to be a film (1) of which temperature was adjusted to 70 ° C., it was heated for 1.5 hours under a surface pressure of 0.1 MPa to obtain a resin supply material (A-6). The volume content Vpi of the continuous porous body (a-3) of this resin supply material (A-6) was 5.6%, the mass content Wpi was 9.4%, and the thickness was 2.3 mm.

Resin supply material (A-7)
Film continuous porous body (a-3) laminate film (300 g / ^{m 2),} and mixtures 1450 g / ^{m 2} (2), the resin (3) / continuous porous body (a-3) / mixture (2) In a press machine laminated at a temperature of 70 ° C. and heated to 1.5 ° C. for 1.5 hours under a surface pressure of 0.1 MPa, a resin supply material (A-7) was obtained. The volume content Vpi of the continuous porous body (a-3) of the resin supply material (A-7) was 5.6%, the mass content Wpi was 9.2%, and the thickness was 2.3 mm.

Resin supply material (A-8)
Film continuous porous body (a-3) a laminate of (300 g / ^{m 2)} and of a mixture of 1450 g / ^{m 2} film (3), the resin (3) / continuous porous body (a-3) / mixture (3) In a press machine laminated at a temperature of 70 ° C. and heated at a surface pressure of 0.1 MPa for 1.5 hours, a resin supply material (A-8) was obtained. The volume content Vpi of the continuous porous body (a-3) of this resin supply material (A-8) was 5.2%, the mass content Wpi was 9.4%, and the thickness was 2.3 mm.

Resin supply material (A-9)
A laminate (300 g / m ² ) of continuous porous body (a-3) and a resin film (1) of 1300 g / m ² are combined into resin film (1) / continuous porous body (a-3) / resin film ( In a press machine laminated to 1) and adjusted to 70 ° C., it was heated for 1.5 hours under a surface pressure of 0.1 MPa to obtain a resin supply material (A-9). The volume content Vpi of the continuous porous body (a-3) of the resin supply material (A-9) was 5.4%, the mass content Wpi was 10.7%, and the thickness was 2.2 mm.

[Base material]
Base material (B-1)
"Trading Cards (registered trademark)" cross, CO6343B (Toray Industries Co., Ltd., plain weave, fiber weight per unit area of 198g ^{/ m} 2)

Base material (B-2)
WF 110D 100 B56 (manufactured by Nittobo Co., Ltd., plain weave, fiber basis weight 97 g / m ² )

Example 1
Resin supply material (A-1) and base material (B-1) 100 mm long and 100 mm wide are composed of 4 layers of base material (B-1) / resin supply material (A-1) / base material (B-1) The preform (D-1) was obtained by laminating to form 4 layers. This preform (D-1) was molded by the following molding method to obtain a fiber reinforced resin (E-1).

Properties of the obtained fiber reinforced resin (E-1) are as shown in Table 11.

(Example 2)
A preform (D-2) and a fiber reinforced resin (E-2) were obtained in the same manner as in Example 1 except that the resin supply material (A-2) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-2).

(Example 3)
A preform (D-3) and a fiber reinforced resin (E-3) were obtained in the same manner as in Example 1 except that the resin supply material (A-3) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-3).

Example 4
A preform (D-4) and a fiber reinforced resin (E-4) were obtained in the same manner as in Example 1 except that the resin supply material (A-4) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-4).

(Example 5)
A preform (D-5) and a fiber reinforced resin (E-5) were obtained in the same manner as in Example 1 except that the resin supply material (A-5) was used. Properties of the obtained fiber reinforced resin (E-5) are as shown in Table 11.

(Example 6)
Resin supply material (A-1) and base material (B-2) 100 mm long and 100 mm wide are composed of 11 layers of base material (B-2) / resin supply material (A-1) / base material (B-1) Lamination was performed so that there were 11 layers to obtain a preform (D-6). This preform (D-6) was molded in the same manner as in Example 1 to obtain a fiber reinforced resin (E-6). Properties of the obtained fiber reinforced resin (E-6) are as shown in Table 11.

(Example 7)
A preform (D-7) and a fiber reinforced resin (E-7) were obtained in the same manner as in Example 6 except that the resin supply material (A-2) was used. Properties of the obtained fiber reinforced resin (E-7) are as shown in Table 11.

(Example 8)
A preform (D-8) and a fiber reinforced resin (E-8) were obtained in the same manner as in Example 6 except that the resin supply material (A-3) was used. Properties of the obtained fiber reinforced resin (E-8) are as shown in Table 11.

Example 9
A preform (D-9) and a fiber reinforced resin (E-9) were obtained in the same manner as in Example 6 except that the resin supply material (A-4) was used. Properties of the obtained fiber reinforced resin (E-9) are as shown in Table 11.

(Example 10)
A preform (D-10) and a fiber reinforced resin (E-10) were obtained in the same manner as in Example 6 except that the resin supply material (A-5) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-10).

(Example 11)
A preform (D-11) and a fiber reinforced resin (E-11) were obtained in the same manner as in Example 6 except that the resin supply material (A-6) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-11).

Example 12
A preform (D-12) and a fiber reinforced resin (E-12) were obtained in the same manner as in Example 6 except that the resin supply material (A-7) was used. Properties of the obtained fiber reinforced resin (E-12) are as shown in Table 11.

(Example 13)
A preform (D-13) and a fiber reinforced resin (E-13) were obtained in the same manner as in Example 6 except that the resin supply material (A-8) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-13).

(Example 14)
Using the preform (D-6) of Example 6, molding was performed by the following molding method.

(1) The preform (D-6) is placed on a metal plate, covered with a film from above, the space between the metal plate and the film is sealed with a sealing material, and a vacuum pump is used for the space covered with the film To a vacuum state (10 ⁻¹ Pa).
(2) While maintaining this state, the inside temperature is put into a dryer whose temperature is adjusted to 70 ° C. and preheated for 10 minutes.
(3) After heating up to 150 ° C. at 3 ° C./min, hold for 40 minutes to cure.

Properties of the obtained fiber reinforced resin (E-14) are as shown in Table 11.

In Examples 1 to 14 described above, by using the resin supply material of the present invention, it was possible to easily produce a fiber reinforced resin without using extra auxiliary materials. In Example 14, it was confirmed that the material was suitable for a molding method capable of molding a low pressure, complex shape such as vacuum pressure molding. Moreover, the fiber reinforced resin excellent in heat conductivity compared with the comparative example 1 was able to be obtained.

From comparison between Examples 8 to 10 and Examples 11 to 13, it can be seen that the fiber-reinforced resin exhibits particularly excellent thermal conductivity when both the first and second modes of the present invention are provided. From a comparison between Example 1 and Example 2, it can be seen that when the thermal conductivity of the material forming the continuous porous body is 50 W / m · K or more, the fiber-reinforced resin exhibits particularly excellent thermal conductivity.

(Comparative Example 1)
A preform (D-15) and a fiber reinforced resin (E-15) were obtained in the same manner as in Example 6 except that the resin supply material (9) was used. Table 11 shows the properties of the obtained fiber reinforced resin (E-15). In Comparative Example 1, although the fiber reinforced resin could be easily produced, the thermal conductivity was inferior to that in the case where the resin supply material of the present invention was used.

The resin supply material of the present invention and the method for producing a fiber reinforced resin using the resin supply material are suitably used for sports applications, general industrial applications, and aerospace applications. More specifically, in general industrial applications, structural materials such as automobiles, ships, and windmills, semi-structured materials, roofing materials, electronic trays such as IC trays and housings of laptop computers, and repair and reinforcement materials. Preferably used. In aerospace applications, it is suitably used for structural materials such as aircraft, rockets, and artificial satellites, and semi-structured materials.

DESCRIPTION OF SYMBOLS 1 Resin supply material 2 Base material 3 Preform 4 Arm 5 Continuous porous body 6 Claw 7 Clamp 8 Cantilever type testing machine 9 Weight P Front end of platform

Claims

A resin supply material used for molding a fiber reinforced resin, comprising a continuous porous body and a resin, wherein the bending resistance Grt of the continuous porous body at 23 ° C. is 10 mN · cm or more, and is represented by the following formula: A resin supply material having a bending resistance ratio Gr of 0.7 or less.
Gr = Gmt / Grt
Gmt: Bending softness of continuous porous body at 70 ° C
The resin supply material according to claim 1, wherein the continuous porous body has a bending length Crt at 23 ° C of 5 cm or more.
The resin supply material according to claim 1 or 2, wherein a minimum tensile strength σmin of the continuous porous body is 3 MPa or more.
The resin supply material according to any one of claims 1 to 3, wherein an elastic modulus Ert of the resin at 23 ° C is 1 MPa or more.
The resin according to any one of claims 1 to 4, wherein the rate of change P before and after molding of the mass of the resin represented by the following formula falls within a range of 0.03 to 0.99. Feed material.
P = Wr2 / Wr1
Wr1: Resin mass in the resin supply material before molding Wr2: Resin mass in the resin supply material after molding
When the minimum tensile strength σmin of the continuous porous body and the tensile strength σo in the direction orthogonal to the direction of the minimum tensile strength are set, the tensile strength ratio σr of the continuous porous body calculated from the following formula is 1. The resin supply material according to any one of claims 1 to 5, which is within a range of 0.0 to 1.2.
σr = σo / σmin
A resin supply material used for molding a fiber reinforced resin, comprising a continuous porous body and a resin, wherein the continuous porous body has a tensile strength σrt of 0.5 MPa or more at 23 ° C. and is represented by the following formula: A resin supply material having a tensile strength ratio σr of 0.5 or more.
σr = σmt / σrt
σmt: Tensile strength of continuous porous body at 130 ° C
The resin supply material according to claim 7, wherein a tensile strength ratio σrtr of the continuous porous body at 23 ° C represented by the following formula is in a range of 0.8-1.
σrtr = σrt / σrtmax
σrtmax: Maximum tensile strength of continuous porous body at 23 ° C.
The resin supply material according to claim 7 or 8, wherein a rate of change P before and after molding of the mass of the resin represented by the following formula falls within a range of 0.03 to 0.99.
P = Wr2 / Wr1
Wr1: Resin mass in the resin supply material before molding Wr2: Resin mass in the resin supply material after molding
The resin supply material according to any one of claims 7 to 9, wherein an elastic magnification Eb of the continuous porous body is within a range of 0.8 to 1.
A resin supply material used for molding a fiber reinforced resin, comprising a continuous porous body and a resin, wherein the material forming the continuous porous body has a thermal conductivity of 1.2 W / m · K or more, and / or Alternatively, a resin supply material including a continuous porous body, a resin, and a filler having a thermal conductivity of 1.2 W / m · K or more.
The resin supply material according to claim 11, wherein a volume content of the filler with respect to the resin is 1% or more and 30% or less.
The resin supply material according to any one of claims 1 to 12, wherein the continuous porous body is formed of reinforcing fibers.
The resin supply material according to claim 13, wherein the reinforcing fiber is selected from at least one selected from carbon fiber, metal fiber, silicon carbide fiber, and silicon nitride fiber.
A preform comprising the resin supply material according to any one of claims 1 to 14 and a base material.
The preform according to claim 15, wherein the base material is at least one base material selected from a woven base material made of reinforcing fibers, a unidirectional base material, and a mat base material.
A method for producing a fiber reinforced resin, in which the preform is heated and pressurized to supply the resin from the resin supply material to the base material and to mold the preform.